Method for iterative n-c and c-c bond formation

Abstract

Disclosed are methods of performing iterative N-C and C-C bond formation, methods of making compounds which enable iterative N-C and C-C bond formation, and compounds which enable iterative N-C and C-C bond formation.

Description

[0001]UIX-05025 METHOD FOR ITERATIVE N-C AND C-C BOND FORMATION RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Application No. 63 / 569,496, filed March 25, 2024; the contents of which is incorporated by reference. STATEMENT OF GOVERNMENT SUPPORT This invention was made with government support under 2019897 awarded by the National Science Foundation. The government has certain rights in the invention. BACKGROUND MIDA and TIDA boronates are used as carbon-based iteration-enabling groups that reversibly attenuate the reactivity of carbon atoms and enable generalized purification via catch and release chromatography. This enables modules to be linked iteratively via C-C bonds. Module- linking N-C bonds also appear in many types of medicines, materials, and other functional molecules, but the ability to iteratively connect modules with a nitrogen, instead of a carbon, atom as the iteration handle, remained an unresolved challenge. The required bifunctional halo-amino building blocks would undergo uncontrolled oligomerization under cross-coupling conditions and known N-protecting groups would not enable generalized purification compatible with automation. In view of the foregoing, there is an unmet need to develop a nitrogen iteration handle. SUMMARY OF THE INVENTION In certain aspects, provided herein are methods of making a compound of formula (I): (I); comprising combining a compound of formula (II): FH12768200.3 UIX-05025 (II); and a compound of formula (III): (III); thereby forming the compound of Formula I; wherein: A is aryl or heteroaryl; E is aryl or heteroaryl; B is a boron having sp3hybridization; n is an integer selected from 1, 2, 3, or 4; m is an integer selected from 0, 1, 2, 3, or 4; X1is halogen or -ORj; X2is halogen; Rjis selected from the group consisting of alkyl, nitrophenyl, pentafluorophenyl, and -N(C(O)CH2)2; R20is selected from the group consisting of H, alkyl, cycloalkyl, alkenyl, alkynyl, and aryl; R21is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R22is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R23is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R24is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; FH12768200.3 UIX-05025 R25is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, halogen, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl; and R26is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl. In further aspects, provided herein are compounds of Formula (I): or a salt thereof; wherein: A is aryl or heteroaryl; B is a boron having sp3hybridization; n is an integer selected from 1, 2, 3, or 4; X1is halogen or ORj; Rjis selected from the group consisting of alkyl, nitrophenyl, pentafluorophenyl, and -N(C(O)CH2)2; R20is selected from the group consisting of H, alkyl, cycloalkyl, alkenyl, alkynyl, and aryl; R21is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, and heteroaryl; R22is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, and heteroaryl; R23is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, and heteroaryl; R24is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, and heteroaryl; and R25is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, halogen, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl. In yet further aspects, provided are methods of making a compound of Formula (I), wherein the method comprises combining a compound of Formula (XII): FH12768200.3 UIX-05025 (XII); and a compound of Formula (XIII): (XIII); thereby forming a compound of Formula (XIV): (XIV); and further combining the compound of Formula (XIV) and a compound of Formula (XV): (XV); thereby forming the compound of Formula (I); wherein: A is aryl or heteroaryl; B is a boron having sp3hybridization; n is an integer selected from 1, 2, 3, or 4; X1is halogen or ORj; Rjis nitrophenyl; R20is selected from the group consisting of H, alkyl, cycloalkyl, alkenyl, alkynyl, and aryl; R21is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R22is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; FH12768200.3 UIX-05025 R23is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R24is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R25is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, halogen, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl; R30is haloalkyl or nitrophenyl; and R31is –(O)haloalkyl or halogen. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A shows molecules inaccessible via iterative cross-coupling due to lack of an N- iteration-enabling group. FIG.1B shows a schematic of the installation of CBzT-Cl on free amines. FIG. 1C shows a schematic demonstrating that CBzT enables iterative and automated N- C bond formation. FIG.1D shows a schematic of iterative automated C-N bond formation as enabled by CBzT. FIG.2A shows a schematic of the synthesis and installation of CBzT. FIG.2B shows an example of catch-and-release purification of a CBzT-amine. FIG.2C shows thin-layer chromatography results of a catch-and-release purification of a CBzT-amine. FIG.2D shows an example of catch-and-release purification for a Buchwald-Hartwig coupling. FIG.3A shows a schematic of the purification of amines with a tolBTIDA byproduct. FIG.3B shows an example of the purification of amines with a p-cresol byproduct. FIG.3C shows an example of “catch and kill” purification. FIG.4 shows images of the automated platform for iterative N-C and C-C bond formation. FIG.5 shows the crystal structure of CBzT-Cl, as solved through X-ray diffraction. FIG.6 shows the crystal structure of compound 5, as solved through X-ray diffraction. FH12768200.3 UIX-05025 FIG.7 shows the crystal structure of compound 8, as solved through X-ray diffraction. FIG.8 shows the crystal structure of compound 19, as solved through X-ray diffraction. FIG.9A shows the results of a thin-layer chromatography experiment demonstrating that CBzT-amines show binary elution properties on silica gel. FIG.9B shows the results of a thin-layer chromatography experiment demonstrating that CBz-amines lack binary elution properties on silica gel. FIG.10 shows the design of the anhydrous automated reaction module. FIG.11 shows the design of the aqueous automated reaction module. FIG.12 shows the design of the catch-and-release purification module. FIG.13 shows proton NMR spectra comparing an imatinib standard to a sample produced via automated synthesis. DETAILED DESCRIPTION OF THE INVENTION Small molecule solutions to many contemporary societal challenges await discovery, but the artisanal and manual process via which this class of chemical manner is typically accessed limits the discovery of new functions. Automated iterative cross-coupling with MIDA or TIDA boronates alternatively enables generalized and automated preparation of many different types of small molecules. But in its current form, this engine cannot leverage nitrogen atoms as iteration handles. Here, a new iteration-enabling group, CbzT, is disclosed, that reversibly attenuates the reactivity of nitrogen atoms and enables generalized catch and release purification. CBzT is leveraged to achieve the automated modular synthesis of Imatinib (Gleevec), an archetypical clinically approved kinase inhibitor, in which building blocks are iteratively linked by both N-C and C-C bonds. This work substantially expands the types of small molecules that can be made in an automated modular fashion. It also advances the concept of intentionally developing chemistry that machines can do. Small molecules are represented as powerful tools with largely untapped potential to help solve frontier societal challenges in the fields of medicine, materials, energy, agriculture, and more. Many such compounds can be viewed as collections of functional modules connected via C-C and N-C bonds (FIG.1A). However, the highly customized, specialist-dependent, and manual process typically utilized to synthesize such compounds hinders the ability to rapidly discover novel small molecule functions. In contrast, the synthesis of biopolymers / oligomers such as polypeptides, oligonucleotides, and oligosaccharides can now be performed automatically. These FH12768200.3 UIX-05025 platforms represent modular synthesis engines in which prefabricated building blocks are iteratively linked using a bounded set of chemical reactions and a general purification strategy. A similar approach to generate small molecules, dubbed iterative cross-coupling (ICC), has emerged and its modularity makes it inherently automatable. This platform has enabled the modular synthesis of many different types of small molecules with myriad functions. Considering that multi-step synthesis automation has the potential to accelerate the discovery of new functional molecules while also allowing non-experts to construct molecules for their unique applications, the expansion of ICC and automation to new functional spaces represents an important step towards democratizing small molecule synthesis. ICC leverages halogen- and boron-containing bifunctional building blocks (called haloboronic acids), increasingly general iterative Suzuki- Miyaura cross-coupling reactions, and a general purification strategy. Specifically, MIDA and TIDA boronates are used as carbon-based iteration-enabling groups that reversibly attenuate the reactivity of carbon atoms and enable generalized purification via "catch-and-release" chromatography. This enables functional modules to be linked iteratively via C-C bonds using iterative cycles of coupling (C), purification (P), and deprotection (D). Module-linking N-C bonds also appear in many types of medicines, materials, and other functional molecules (FIG. 1A), but the ability to iteratively connect modules with a nitrogen, instead of a carbon, atom as the iteration handle remained an unresolved challenge. The required bifunctional halo-amine building blocks would undergo potential uncontrolled oligomerization and other undesired side reactions under cross-coupling conditions, and known N-protecting groups would not enable generalized purification compatible with automation (FIG.1B). Herein, a novel reagent, p-TIDA boronate-substituted benzyl chloroformate (CbzT-Cl) (1) (FIG. 1C), is described that enables iterative N-C bond formation by reversibly attenuating the reactivity of amines and permitting automation-friendly generalized purification via "catch-and-release" chromatography (FIG.1D). To add N-C bond formation into the ICC strategy, incorporation of a general purification handle, in the form of the highly stable TIDA boronate group, into a robust and well-characterized nitrogen protecting group was specifically envisioned. It was anticipated that such an iteration enabling group would both prevent undesired oligomerization and enable generalized and automated purification due to the remarkably general binary elution properties of TIDA boronates on silica gel. After surveying common amine protecting groups, benzyl chloroformate was identified as an especially promising scaffold due to its easily modifiable core FH12768200.3 UIX-05025 structure, ease of introduction with a wide range of amines, the expected stability of the corresponding benzyl carbamates under cross-coupling conditions, and the facility with which such motifs can be removed under orthogonal conditions. Synthesis of CbzT chloride (1) proceeded via TIDA complexation of (4- (hydroxymethyl)phenyl)boronic acid followed by nucleophilic substitution of triphosgene (FIG. 2A). CbzT-Cl is a crystalline, bench stable solid that was prepared on gram scale and stored on a benchtop in a sealed vial under air. Additionally, it can be prepared and used directly after concentration of the crude reaction mixture without further purification. A variety of bases were tested for the installation of CbzT onto 3-bromoaniline (4), but most of these provided a mixture of undesired byproducts such as the benzyl chloride, akin to previous reports. Potassium phosphate provided 66% yield of the desired CbzT protected amine (5), but exogenous base-free conditions afforded the highest yield of 90% (FIG.2B). Additionally, in some cases it was found that CbzT- carbonate (S2) can provide increased yields compared to the CbzT-Cl (1), although 1 is more general across the scope of amines tested. With bifunctional block 5 in hand, it was first tested if the targeted chemoselective coupling step could be achieved. It was specifically asked if bifunctional halo-CbzT-amines could be engaged as electrophiles in cross-coupling with chemoselective reactivity at the halide terminus without undesired oligomerization at the amine- terminus. Buchwald-Hartwig cross-coupling of 6 with bifunctional bromo-CbzT-amine 5 proceeded with high efficiency for the desired product 7 (FIG.2C). The purification step was next tested. It was hypothesized that CbzT groups would exhibit the same binary affinity for silica gel that enable C-centered MIDA and TIDA boronates to be purified via general and machine-friendly "catch-and-release" chromatography (FIG.2D). This hypothesis was confirmed via TLC analysis of a variety of CbzT-amines, while Cbz-amines submitted to the same conditions did not show binary elution properties. "Catch-and-release" purification of the crude reaction mixture from the reaction of 5 and 6 was also attempted and 7 was obtained in 70% yield and high purity. Specifically, the mixture derived from the coupling of 5 and 6 was loaded onto a silica gel plug and then byproducts / impurities were removed by eluting with diethyl ether. During this step, the cross-coupling product (7) containing the CbzT-group was retained on the silica gel. A second elution with a more polar solvent (ethyl acetate) was then performed, releasing purified product 7 (FIG. 2D) (Similar results were obtained using acetone as the release solvent). The deprotection FH12768200.3 UIX-05025 of TIDA boronates only yields TIDA as a byproduct, which is easily removed during an aqueous work-up. To complete the targeted iterable sequence of coupling, purification, and deprotection sequence, ways to deprotect CbzT-amines while creating product mixtures that could be purified in a simple and automation-friendly manner were explored. Two alternative strategies relying on conversion of CbzT into volatile CO2and other easily removed byproduct were ideated. In the first approach, the use of Pd-mediated hydrogenation to cleave the CbzT group and generate tolyl TIDA boronate (tolBTIDA, 10) (FIG.3A) was targeted. Simple removal of 10 using silica gel as a capture resin was anticipated. After screening a variety of conditions (Example 2), it was found that the deprotection of 8 was achieved in an automation-friendly way via treatment with catalytic palladium on carbon and sodium borohydride in >90% yield (Example 2 entries 2,3). Similar results were obtained with 7 (Example 2). Subsequent purification of product 12 was achieved by running the optimized deprotection conditions on 7, loading the crude reaction mixture onto a silica plug with hexanes and flushing with Et2O to elute the free amine 12 while retaining TIDA boronate-containing 10 on the silica plug. This simple procedure afforded purified 12 in 93% isolated yield and excellent purity. In the second approach, an alternative protocol to provide flexibility for substrates that may not be compatible with reactions mediated by unligated palladium, such as those that are rich in heteroatoms, was sought. Conditions that would similarly liberate CO2but alternatively generate p-cresol 11 as a byproduct (FIG.3B), which could presumably be separated with a silica gel plug due to its anticipated decreased polarity relative to free amine products, were specifically envisioned. In this vein, it was found that hydrolysis and oxidation of the TIDA boronic ester using LiOH / H2O2liberated p-cresol 11 and desired free amine products for both 8 and 7 (Example 2). The corresponding free amine products were readily purified via silica plug by first eluting p- cresol and other undesired reaction byproducts with hexanes, and then releasing the free amine using diethyl ether. Having developed methods to complete the targeted couple, purify, and deprotect sequences, it was tested if the CbzT protecting group could enable iterative N-C and / or C-C bond formation. Two trimers were first aimed to be manually generated, the first of these requiring two iterative N-C bond forming reactions and the second requiring C-C bond followed by N-C bond formation (Example 3). Synthesis of the first trimer proceeded via the previously described Buchwald-Hartwig cross-coupling of 6 with bifunctional CbzT-protected haloamine 5 followed FH12768200.3 UIX-05025 by "catch-and-release" purification to provide 7. Deprotection of 7 with removal of 10 using silica gel as a capture resin proceeded smoothly to provide purified 12. The free amine product (12) was then submitted to amide bond formation conditions with benzoic acid (13) to forge trimer 14 in 45% yield. Synthesis of the second trimer proceeded via Suzuki-Miyaura cross-coupling of pinacol boronic ester 15 with 5 and then "catch-and-release" purification to obtain the purified dimeric coupling product (16) in >90% yield. Deprotection and silica gel capture-mediated removal of 10 provided free amine 17 in >90% yield. Subsequent Buchwald-Hartwig coupling with bromobenzene (18) produced the desired trimer product (19) in 95% yield. In most cases, "catch-and-release" purification yields products with very high purity. In cases where minor impurities are present, they are not significant enough to affect the outcome of subsequent reactions. Having established the viability of the newly developed N-C and / or C-C bond forming iterative cross-coupling platform, a new synthesis machine capable of automatically executing the coupling, deprotection, and purification steps described above was constructed (FIG.5). Building on previous advances from the group, the synthesis machine integrates several key components via a LabVIEW interface: 40 mL scintillation vials as reaction vessels, hot plates with aluminum blocks for heating and magnetic stirring, disposable "catch-and-release" cartridges, a syringe pump for liquid transfer, multiport valve assemblies, and a rotary evaporator system for solvent evaporation. The system maintains an argon atmosphere through an automated Schlenk protocol enabled by a high vacuum pump that also serves vacuum-driven fluid transfer. Leveraging this synthesis machine and the established coupling, purification, and deprotection protocols, an additional three trimers were set out to be constructed, this time in a fully automated manner (Example 5). First, trimers 25, 30 and 36 were synthesized manually with intermediate isolated and characterized. Then, these synthetic procedures were translated to the synthesis machine and performed in series without any characterization of intermediates. Synthesis of the trimer 25 proceeded via Suzuki-Miyaura cross-coupling of pinacol boronic ester 20 with bifunctional CbzT- protected haloamine 21 and then "catch-and-release" purification to obtain the purified dimer product (20) in >90% yield. Deprotection and silica gel capture-mediated to remove 10 provided free amine 23 in 90% yield. Subsequent amide coupling with benzoyl chloride (24) resulted in the desired trimer product (25) in 88% yield. FH12768200.3 UIX-05025 Synthesis of trimer 30 proceeded via Suzuki-Miyaura cross-coupling of boronic acid neopentylglycol ester 26 with bifunctional CbzT-protected haloamine 5 and then "catch-and- release" purification to obtain the dimeric coupling product (27) in >90% yield. Deprotection provided free amine 28 in 40% yield. Amide coupling with pentanoyl chloride (29) produced the desired trimer product (30) in 35% yield. Synthesis of trimer 36 proceeded via the Buchwald- Hartwig cross-coupling of 31 with bifunctional CbzT-protected haloamine 32 followed by "catch- and-release" purification to provide 33 in 84% yield. Deprotection of 33 provided 34 in 38% yield. The free amine product (34) was submitted to another Buchwald-Hartwig cross-coupling with halogen 35 to forge the trimer 36 in 52% yield. Notably, all three of these automated modular syntheses afforded >10 mg of the purified trimer products. Finally, an FDA approved kinase inhibitor rich in N-C and C-C bond-based module connections was set out to be automatically synthesized. Kinase inhibitors represent a very important subset of anticancer drugs that could in theory be rapidly accessed via the automated iterative cross-coupling strategy. Notably, more than 90% of the 538 human kinases have not yet been drugged. Imatinib (Gleevec®) was identified as an archetypical test for the new platform (Example 6). This molecule posed a notable challenge because it required three difficult coupling reactions with heterocyclic building blocks, highly polar and thus challenging-to-purify intermediates, and many heteroatom-rich intermediates that could be incompatible with hydrogenation-based deprotection mediated by unligated palladium. Before fully automating the process, the proposed route was tested by hand and then each step was automated independently. Common Suzuki-Miyaura conditions were found to be unproductive for the coupling of 37 and 38, likely due to well established challenges representative of heterocyclic substrates. Use of a variant of Denmark and coworkers' TMSOK-promoted coupling conditions, recently shown to be compatible with TIDA boronate-enabled automated synthesis, provided the desired coupling product (39) in 54% manual yield and 42% automated yield. Removal of the CbzT-group via treatment with Pd / NaBH4 followed by a modified sequence of eluents appropriate for such a polar product, generated free amine 40 in 75% manual yield and 50% automated yield. This amine was then engaged in a Buchwald-Hartwig coupling with CbzT-protected bifunctional haloamine 41 followed by "catch-and-release" purification providing the coupling product 42 in 60% manual yield and 55% automated yield. Heteroatom-rich intermediate (42) exhibited resistance to deprotection when using the Pd-mediated conditions. An opportunity to use the alternative FH12768200.3 UIX-05025 LiOH / H2O2procedure and telescope into the final amide bond formation was recognized. The hydrolysis-oxidation-deprotection was successful, providing 43 in 60% manual yield and 49% automated yield. Free amine 43 was subjected to amide bond-forming conditions with 44, providing Imatinib in 68% manual yield and 60% automated yield. The lower automated yield may be due to loss of material that occurs when solutions are transferred between vessels through tubing. This process was then performed in a fully automated manner on the next-generation synthesis machine described above without any analytics or isolation of intermediates to yield 2 mg of imatinib after a final HPLC-based purification. This product was suitable in quantity and purity for what is required for testing in biological assays, which are now routinely conducted in miniaturized formats. In conclusion, a novel automation friendly iteration enabling group that reversibly attenuates the reactivity of amines while simultaneously enabling automated purification by "catch-and-release" chromatography was developed. The utility of this synthetic platform was demonstrated via the automated modular synthesis of imatinib, an archetypical kinase inhibitor. This expanded automated modular synthesis approach stands to enable the on-demand synthesis and testing of a wide range of drug candidates and incorporation of such capacity into AI-guided closed-loop discovery engines, similar to the way organic materials discovery has recently been enabled by automated modular small molecule synthesis. The CbzT group also has potential applications in the simplified prefabrication of diverse amine-containing building blocks. Finding increasingly general conditions for coupling, deprotection, and purification is a frontier and unmet challenge in chemical reaction development that will broadly enable automation. Together, this work emphasizes the impact of intentionally developing new synthetic methods explicitly to enable the automation of small molecule synthesis. Methods of C-C / C-N Bond Formation In certain aspects, disclosed herein are methods of making a compound of formula (I): FH12768200.3 UIX-05025 comprising combining a compound of formula (II): (II); and a compound of formula (III): (III); thereby forming the compound of Formula I; wherein: A is aryl or heteroaryl; E is aryl or heteroaryl; B is a boron having sp3hybridization; n is an integer selected from 1, 2, 3, or 4; m is an integer selected from 0, 1, 2, 3, or 4; X1is halogen or -ORj; X2is halogen; Rjis selected from the group consisting of alkyl, nitrophenyl, pentafluorophenyl, and -N(C(O)CH2)2; R20is selected from the group consisting of H, alkyl, cycloalkyl, alkenyl, alkynyl, and aryl; R21is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R22is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R23is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R24is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; FH12768200.3 UIX-05025 R25is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, halogen, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl; and R26is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl. In certain embodiments, the methods further comprise a base selected from the group consisting of triethylamine, pyridine, 2,6-lutidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 2,2,6,6- tetramethylpiperidine, NaHCO3, K2CO3, CsCO3, and K3PO4. In further embodiments, A is phenyl. In yet further embodiments, each of R21, R22, R23, and R24is methyl. In yet further embodiments, each of R20, R21, R22, R23, and R24is methyl. In still further embodiments, R25is H. In certain embodiments, X1is chloro or fluoro. In further embodiments, X1is chloro. In yet further embodiments, X1is ORj. In still further embodiments, Rjis selected from the group consisting of methyl, ethyl, nitrophenyl, pentafluorophenyl, and -N(C(O)CH2)2. In certain embodiments, X2is bromo or iodo. In further embodiments, the methods further comprise combining the compound of Formula (I), a compound of Formula (V): (V); a palladium catalyst, and a base; thereby forming a compound of Formula (IV): (IV); wherein: G is aryl or heteroaryl; p is an integer selected from 0, 1, 2, 3, and 4; FH12768200.3 UIX-05025 R27is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, halogen, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl; Y1is selected from the group consisting of -NH2, -B(pin), -B(neop), -B(dan), -B(MIDA), and -B(OH)2; and Y2is -NH- or is a bond. In yet further embodiments, Y1is -NH2. In still further embodiments, Y1is -B(OH)2. In certain embodiments, Y2is -NH-. In further embodiments, Y2is a bond. In yet further embodiments, the palladium catalyst is a Buchwald precatalyst. Buchwald precatalysts are transition metal complexes used in, for example, cross-coupling reactions, and are of the general form (L(M) G1–G4), wherein L is a ligand, M is a transition metal, such as palladium, and G indicates the generational series, for example, (XPhos)Pd G3. A list of transition metal catalysts, including Buchwald precatalysts, used in this disclosure and their standard nomenclature follows below. In still further embodiments, the palladium catalyst is selected from the group consisting of (t-Bu-XPhos)Pd G3 [(2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′- amino-1,1′-biphenyl)] palladium(II) methanesulfonate], (t-Bu-XPhos)Pd G4 [(SP-4-3)-[2-di-tert- butylphosphino-2′,4′,6′-triisopropylbiphenyl[1,1′-biphenyl]-2-yl]phosphine](methanesulfonato- κO)[2′-(methylamino-κN)[1,1′-biphenyl]-2-yl-κC]palladium], (XPhos)Pd G3 [(2- dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)] palladium(II) methanesulfonate], (XPhos)Pd G4 [(SP-4-3)-[dicyclohexyl[2′,4′,6′-tris(1- methylethyl)[1,1′-biphenyl]-2-yl]phosphine](methanesulfonato-κO)[2′-(methylamino-κN)[1,1′- biphenyl]-2-yl-κC]palladium], Pd(PPh3)4 [tetrakis(triphenylphosphine)palladium(0)], (RuPhos)Pd G3 [(2-dicyclohexylphosphino-2′,6′-diisopropoxy-1,1′-biphenyl)[2-(2′-amino-1,1′- biphenyl)]palladium(II) methanesulfonate], (RuPhos)Pd G4 [[dicyclohexyl(2′,6′-diisopropoxy-2- biphenylyl)phosphine-κP](methanesulfonatato-κO)[2′-(methylamino-κN)-2-biphenylyl- κC2]palladium], (XantPhos)Pd G3 [[(4,5-bis(diphenylphosphino)-9,9-dimethylxanthene)-2-(2′- amino-1,1′-biphenyl)]palladium(II) methanesulfonate], (XantPhos)Pd G4 [(SP-4-3)-[[5- (diphenylphosphino)-9,9-dimethyl-9H-xanthen-4-yl]diphenylphosphine-κP](methanesulfonato- κO)[2′-(methylamino-κN)[1,1′-biphenyl]-2-yl-κC]- palladium], (t-Bu-P)3Pd G3 [(tris(2-methyl-2- propanyl)phosphino-2′,6′-diisopropoxy-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II) methanesulfonate], (t-Bu-P)3Pd G4 [(methanesulfonatato-κO)[2′-(methylamino-κN)-2- FH12768200.3 UIX-05025 biphenylyl-κC2][tris(2-methyl-2-propanyl)phosphine]palladium], (Sphos)Pd G3 [(2- dicyclohexylphosphino-2′,6′-dimethoxybiphenyl) [2-(2′-amino-1,1′-biphenyl)]palladium(II) methanesulfonate], (Sphos)Pd G4 [(methanesulfonato-κO)[2′-(methylamino)-2- biphenylyl]palladium – dicyclohexyl(2′,6′-dimethoxy-2-biphenylyl)phosphine], Pd(Oac)2[palladium(II) acetate], (Pd)2(DBA)3[tris(dibenzylideneacetone)dipalladium(0) ], and Pd(PPh3)2(Cl)2[bis(triphenylphosphine)palladium(II) dichloride]. In preferred embodiments, the palladium catalyst is (t-Bu-XPhos)Pd G3 or (t-Bu-P)3Pd G4. In certain embodiments, the base is selected from the group consisting of potassium trimethylsilanolate, triethylamine, pyridine, 2,6-lutidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 2,2,6,6- tetramethylpiperidine, NaHCO3, K2CO3, CsCO3, and K3PO4. In further embodiments, the base is potassium trimethylsilanolate. In yet further embodiments, the methods further comprise combining the compound of Formula (IV) and a reducing agent, thereby forming a compound of Formula (VI): (VI). In still further embodiments, the reducing agent is selected from the group consisting of BF3•Oet2, EtSH, TBAF, TMSI, Pd / C, H2, and NaBH4, or a combination of any of them. In certain embodiments, the reducing agent is the combination of Pd / C, NaBH4and H2. In further embodiments, the methods further comprise combining the compound of Formula (VI), a compound of Formula (VIII): (VIII); an activating agent, and a base; thereby forming a compound of Formula (VII): FH12768200.3 UIX-05025 (VII); wherein: J is aryl or heteroaryl; q is an integer selected from 0, 1, 2, 3, or 4; R28is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, halogen, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl; Y3is -C(O)2H or a carboxylate salt, and Y4is –C(O)-; or Y3is halogen, and Y4is a bond; when Y3is -CO2H or a carboxylate salt, the activating agent is selected from the group consisting of propylphosphonic anhydride, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, benzotriazole-1-yl-oxy-tris-(dimethylamino)-phosphonium hexafluorophosphate, 1-[(1-(cyano-2- ethoxy-2-oxoethylideneaminooxy) dimethylaminomorpholino)] uronium hexafluorophosphate, hexafluorophosphate azabenzotriazole tetramethyluronium, hexafluorophosphate benzotriazole tetramethyluronium, benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, and benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate; and when Y3is halogen, the activating agent is selected from the group consisting of Pd(Oac)2, (Sphos)Pd(Oac)2, (Sphos)Pd G3, and (Sphos)Pd G4. In yet further embodiments, Y3is CO2H or a carboxylate salt, and the activating agent is propylphosphonic anhydride; or wherein Y3is halogen, and the activating agent is (Sphos)Pd(Oac)2. In still further embodiments, the base is pyridine or Cs2CO3. In certain embodiments, the methods disclosed herein further comprise combining the compound of Formula (VII) and an oxidizing agent, thereby forming a compound of Formula (IX): FH12768200.3 UIX-05025 (IX). In further embodiments, the oxidizing agent is the combination of LiOH and H2O2. In yet further embodiments, the methods disclosed herein further comprise combining the compound of Formula (IX), a compound of Formula (XI): (XI), and a base; thereby forming a compound of Formula (X): (X); wherein: L is aryl or heteroaryl; X3is halogen; s is an integer selected from 0, 1, 2, 3, 4, or 5; and R29is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, heterocyclyl, heterocyclylalkyl, aryl, and heteroaryl. In still further embodiments, the base is pyridine. In certain embodiments, X3is chloro. In further embodiments, L is phenyl. In yet further embodiments, R29is N- methylpiperazinylmethylene. In still further embodiments, s is 1. In certain embodiments, the methods disclosed herein further comprise combining the compound of Formula (VI), a compound of Formula (XII): (XII); and a base; thereby forming a compound of Formula (XIII): FH12768200.3 UIX-05025 (XIII); wherein: L is aryl or heteroaryl; X4is halogen; u is an integer selected from 0, 1, 2, 3, 4, or 5; and R30is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, heterocyclyl, heterocyclylalkyl, aryl, and heteroaryl. In further embodiments, L is aryl. In yet further embodiments, L is phenyl. In still further embodiments, X4is chloro. In certain embodiments, the base is pyridine. In further embodiments, the methods disclosed herein further comprise combining the compound of Formula (VI), a compound of Formula (XIV): (XIV); and a base; thereby forming a compound of Formula (XV): (XV); wherein: X5is halogen; R31is selected from the group consisting of H, alkyl, cycloalkyl, heterocyclyl, and heterocyclylalkyl. In yet further embodiments, X5is chloro. In still further embodiments, R31is alkyl. In certain embodiments, R31is butyl. In further embodiments, the base is pyridine. FH12768200.3 UIX-05025 Compounds of the Disclosure, and Methods of Making Thereof In another aspect, disclosed herein are compounds represented by Formula (I): or a salt thereof; wherein: A is aryl or heteroaryl; B is a boron having sp3hybridization; n is an integer selected from 1, 2, 3, or 4; X1is halogen or ORj; Rjis selected from the group consisting of alkyl, nitrophenyl, pentafluorophenyl, and -N(C(O)CH2)2; R20is selected from the group consisting of H, alkyl, cycloalkyl, alkenyl, alkynyl, and aryl; R21is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, and heteroaryl; R22is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, and heteroaryl; R23is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, and heteroaryl; R24is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, and heteroaryl; and R25is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, halogen, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl. In certain embodiments, A is phenyl. In further embodiments, R25is H. In yet further embodiments, at least one of R21, R22, R23, or R24is not H. In still further embodiments, at least two of R21, R22, R23, or R24are not H. In certain embodiments, at least three of R21, R22, R23, or R24are not H. In further embodiments, none of R21, R22, R23, or R24is H. In yet further embodiments, each of R21, R22, R23, and R24is methyl. In yet further embodiments, each of R20, R21, R22, R23, and R24is methyl. In still further embodiments, X1is chloro or fluoro. In certain embodiments, X1is chloro. In further embodiments, X1is ORj. In yet further embodiments, Rjis selected from the FH12768200.3 UIX-05025 group consisting of methyl, ethyl, nitrophenyl, pentafluorophenyl, and -N(C(O)CH2)2. In still further embodiments, Rjis 4-nitrophenyl. In certain embodiments, the compound is: . In further embodiments, the compound is: . In yet another aspect, disclosed herein are methods of making a compound of Formula (I), wherein the method comprises combining a compound of Formula (XVI): (XVI); and a compound of Formula (XVII): (XVII); thereby forming a compound of Formula (XVIII): (XVIII); and further combining the compound of Formula (XVIII) and a compound of Formula (XIX): FH12768200.3 UIX-05025 (XIX); thereby forming the compound of Formula (I); wherein: A is aryl or heteroaryl; B is a boron having sp3hybridization; n is an integer selected from 1, 2, 3, or 4; X1is halogen or ORj; Rjis nitrophenyl; R20is selected from the group consisting of H, alkyl, cycloalkyl, alkenyl, alkynyl, and aryl; R21is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R22is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R23is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R24is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R25is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, halogen, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl; R30is haloalkyl or nitrophenyl; and R31is –(O)haloalkyl or halogen. In certain embodiments, A is phenyl. In further embodiments, R25is H. In yet further embodiments, X1is chloro or fluoro. In still further embodiments, X1is ORj. In certain embodiments, Rjis 4-nitrophenyl. In yet further embodiments, each of R21, R22, R23, and R24is methyl. In further embodiments, each of R20, R21, R22, R23, and R24is methyl. In yet further embodiments, R30is -C(Cl)3. In still further embodiments, R31is -O(C(Cl)3). In certain embodiments, R30is 4-nitrophenyl. In further embodiments, R31is chloro. In yet further embodiments, the compound of Formula (XVI) is: FH12768200.3 UIX-05025 , or a salt thereof. In still further embodiments, the compound of Formula (XVII) is: , or a salt thereof. In certain embodiments, the compound of Formula (XVIII) is: salt thereof. In further embodiments, the compound of Formula (XIX) is selected from the group consisting of: salt thereof. Definitions The articles “a” and “an” are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, “an element” means one element or more than one element. The term “heteroatom” is art-recognized and refers to an atom of any element other than carbon or hydrogen. Illustrative heteroatoms include boron, nitrogen, oxygen, phosphorus, sulfur and selenium, and alternatively oxygen, nitrogen or sulfur. The term “alkyl” as used herein is a term of art and refers to saturated aliphatic groups, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl substituted cycloalkyl groups, and cycloalkyl substituted alkyl groups. In certain embodiments, a straight-chain or branched-chain alkyl has about 30 or fewer carbon atoms in its backbone (e.g., C1-C30for straight chain, C3-C30for branched chain), and alternatively, about 20 or fewer, or 10 or fewer. In certain embodiments, the term “alkyl” refers to a C1-C10alkyl group. FH12768200.3 UIX-05025 In certain embodiments, the term “alkyl” refers to a C1-C6alkyl group, for example a C1-C6straight-chain alkyl group. In certain embodiments, the term “alkyl” refers to a C3-C12branched- chain alkyl group. In certain embodiments, the term “alkyl” refers to a C3-C8branched-chain alkyl group. Representative examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and n-hexyl. The term “cycloalkyl” means mono- or bicyclic or bridged saturated carbocyclic rings, each having from 3 to 12 carbon atoms. Certain cycloalkyls have from 5-12 carbon atoms in their ring structure, and may have 6-10 carbons in the ring structure. Preferably, cycloalkyl is (C3- C7)cycloalkyl, which represents a monocyclic saturated carbocyclic ring, having from 3 to 7 carbon atoms. Examples of monocyclic cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, and cyclooctyl. Bicyclic cycloalkyl ring systems include bridged monocyclic rings and fused bicyclic rings. Bridged monocyclic rings contain a monocyclic cycloalkyl ring where two non-adjacent carbon atoms of the monocyclic ring are linked by an alkylene bridge of between one and three additional carbon atoms (i.e., a bridging group of the form –(CH2)w-, where w is 1, 2, or 3). Representative examples of bicyclic ring systems include, but are not limited to, bicyclo[3.1.1]heptane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, bicyclo[3.2.2]nonane, bicyclo[3.3.1]nonane, and bicyclo[4.2.1]nonane. Fused bicyclic cycloalkyl ring systems contain a monocyclic cycloalkyl ring fused to either a phenyl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, a monocyclic heterocyclyl, or a monocyclic heteroaryl. The bridged or fused bicyclic cycloalkyl is attached to the parent molecular moiety through any carbon atom contained within the monocyclic cycloalkyl ring. Cycloalkyl groups are optionally substituted. In certain embodiments, the fused bicyclic cycloalkyl is a 5 or 6 membered monocyclic cycloalkyl ring fused to either a phenyl ring, a 5 or 6 membered monocyclic cycloalkyl, a 5 or 6 membered monocyclic cycloalkenyl, a 5 or 6 membered monocyclic heterocyclyl, or a 5 or 6 membered monocyclic heteroaryl, wherein the fused bicyclic cycloalkyl is optionally substituted. The term “(cycloalkyl)alkyl” as used herein refers to an alkyl group substituted with one or more cycloalkyl groups. An example of cycloalkylalkyl is cyclohexylmethyl group. The term “heterocycloalkyl” as used herein refers to a radical of a non-aromatic ring system, including, but not limited to, monocyclic, bicyclic, and tricyclic rings, which can be completely saturated or which can contain one or more units of unsaturation, for the avoidance of FH12768200.3 UIX-05025 doubt, the degree of unsaturation does not result in an aromatic ring system, and having 3 to 12 atoms including at least one heteroatom, such as nitrogen, oxygen, or sulfur. For purposes of exemplification, which should not be construed as limiting the scope of this invention, the following are examples of heterocyclic rings: aziridinyl, azirinyl, oxiranyl, thiiranyl, thiirenyl, dioxiranyl, diazirinyl, diazepanyl, 1,3-dioxanyl, 1,3-dioxolanyl, 1,3-dithiolanyl, 1,3-dithianyl, imidazolidinyl, isothiazolinyl, isothiazolidinyl, isoxazolinyl, isoxazolidinyl, azetyl, oxetanyl, oxetyl, thietanyl, thietyl, diazetidinyl, dioxetanyl, dioxetenyl, dithietanyl, dithietyl, dioxalanyl, oxazolyl, thiazolyl, triazinyl, isothiazolyl, isoxazolyl, azepines, azetidinyl, morpholinyl, oxadiazolinyl, oxadiazolidinyl, oxazolinyl, oxazolidinyl, oxopiperidinyl, oxopyrrolidinyl, piperazinyl, piperidinyl, pyranyl, pyrazolinyl, pyrazolidinyl, pyrrolinyl, pyrrolidinyl, quinuclidinyl, thiomorpholinyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothienyl, thiadiazolinyl, thiadiazolidinyl, thiazolinyl, thiazolidinyl, thiomorpholinyl, 1,1- dioxidothiomorpholinyl (thiomorpholine sulfone), thiopyranyl, trithianyl, and 2- azobicyclo[3.1.0]hexane. A heterocycloalkyl group is optionally substituted by one or more substituents as described below. The term “(heterocycloalkyl)alkyl” as used herein refers to an alkyl group substituted with one or more heterocycloalkyl (i.e., heterocyclyl) groups. The term “alkenyl” as used herein means a straight or branched chain hydrocarbon radical containing from 2 to 10 carbons and containing at least one carbon-carbon double bond formed by the removal of two hydrogens. Representative examples of alkenyl include, but are not limited to, ethenyl, 2-propenyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, 5-hexenyl, 2-heptenyl, 2- methyl-1-heptenyl, and 3-decenyl. The unsaturated bond(s) of the alkenyl group can be located anywhere in the moiety and can have either the (Z) or the (E) configuration about the double bond(s). The term “alkynyl” as used herein means a straight or branched chain hydrocarbon radical containing from 2 to 10 carbon atoms and containing at least one carbon-carbon triple bond. Representative examples of alkynyl include, but are not limited, to acetylenyl, 1-propynyl, 2- propynyl, 3-butynyl, 2-pentynyl, and 1-butynyl. The term “alkylene” is art-recognized, and as used herein pertains to a diradical obtained by removing two hydrogen atoms of an alkyl group, as defined above. In one embodiment an alkylene refers to a disubstituted alkane, i.e., an alkane substituted at two positions with FH12768200.3 UIX-05025 substituents such as halogen, azide, alkyl, arylalkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aromatic or heteroaromatic moieties, fluoroalkyl (such as trifluromethyl), cyano, or the like. That is, in one embodiment, a “substituted alkyl” is an “alkylene”. The term “amino” is a term of art and as used herein refers to both unsubstituted and substituted amines, e.g., a moiety that may be represented by the general formulas: wherein Ra, Rb, and Rceach independently represent a hydrogen, an alkyl, an alkenyl, -(CH2)x-Rd, or Raand Rb, taken together with the N atom to which they are attached complete a heterocycle having from 4 to 8 atoms in the ring structure; Rdrepresents an aryl, a heteroaryl, a cycloalkyl, a cycloalkenyl, a heterocyclyl or a polycyclyl; and x is zero or an integer in the range of 1 to 8. In certain embodiments, only one of Raor Rbmay be a carbonyl, e.g., Ra, Rb, and the nitrogen together do not form an imide. In other embodiments, Raand Rb(and optionally Rc) each independently represent a hydrogen, an alkyl, an alkenyl, or –(CH2)x-Rd. In certain embodiments, Raand Rbare each independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, (cycloalkyl)alkyl, (heterocycloalkyl)alkyl, arylalkyl, heteroarylalkyl, alkoxyalkyl, or haloalkyl, any of which may be further substituted (e.g., by halogen, alkyl, alkoxy, hydroxy, and so forth). In certain embodiments, the term “amino” refers to –NH2. In certain embodiments, the term “alkylamino” refers to -NH(alkyl). In certain embodiments, the term “dialkylamino” refers to -N(alkyl)2. The term “amido”, as used herein, means -NHC(=O)-, wherein the amido group is bound to the parent molecular moiety through the nitrogen. Examples of amido include alkylamido such as CH3C(=O)N(H)- and CH3CH2C(=O)N(H)-. The term “acyl” is a term of art and as used herein refers to any group or radical of the form RCO- where R is any organic group, e.g., alkyl, aryl, heteroaryl, arylalkyl, and heteroarylalkyl. Representative acyl groups include acetyl, benzoyl, and malonyl. FH12768200.3 UIX-05025 The term “aminoalkyl” as used herein refers to an alkyl group substituted with one or more one amino groups. In one embodiment, the term “aminoalkyl” refers to an aminomethyl group, i.e., -CH2NH2. The term “aminoacyl” is a term of art and as used herein refers to an acyl group substituted with one or more amino groups. The term “aminothionyl” as used herein refers to an analog of an aminoacyl in which the O of RC(O)- has been replaced by sulfur, hence is of the form RC(S)-. The term “phosphoryl” is a term of art and as used herein may in general be represented by the formula: wherein Q50 represents S or O, and R59 represents hydrogen, a lower alkyl or an aryl; for example, -P(O)(Ome)- or -P(O)(OH)2. When used to substitute, e.g., an alkyl, the phosphoryl group of the phosphorylalkyl may be represented by the general formulas: Q50 Q50 Q51 P O Q51 POR59 OR59 OR59 ; wherein Q50 and R59, each independently, are defined above, and Q51 represents O, S or N; for example, -O-P(O)(OH)Ome or -NH-P(O)(OH)2. When Q50 is S, the phosphoryl moiety is a “phosphorothioate.” The term “aminophosphoryl” as used herein refers to a phosphoryl group substituted with at least one amino group, as defined herein; for example, -P(O)(OH)Nme2. The term “azide” or “azido”, as used herein, means an –N3group. The term “carbonyl” as used herein refers to -C(=O)-. The term “thiocarbonyl” as used herein refers to -C(=S)-. The term “alkylphosphoryl” as used herein refers to a phosphoryl group substituted with at least one alkyl group, as defined herein; for example, -P(O)(OH)Me. The term “alkylthio” as used herein refers to alkyl-S-. The term “(alkylthio)alkyl” refers to an alkyl group substituted by an alkylthio group. The term “carboxy”, as used herein, means a -CO2H group. FH12768200.3 UIX-05025 The term “aryl” is a term of art and as used herein refers to includes monocyclic, bicyclic and polycyclic aromatic hydrocarbon groups, for example, benzene, naphthalene, anthracene, and pyrene. Typically, an aryl group contains from 6-10 carbon ring atoms (i.e., (C6-C10)aryl). The aromatic ring may be substituted at one or more ring positions with one or more substituents, such as halogen, azide, alkyl, arylalkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aromatic or heteroaromatic moieties, fluoroalkyl (such as trifluromethyl), cyano, or the like. The term “aryl” also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings (the rings are “fused rings”) wherein at least one of the rings is an aromatic hydrocarbon, e.g., the other cyclic rings may be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and / or heterocyclyls. In certain embodiments, the term “aryl” refers to a phenyl group. The term “heteroaryl” is a term of art and as used herein refers to a monocyclic, bicyclic, and polycyclic aromatic group having 3 to 12 total atoms including one or more heteroatoms such as nitrogen, oxygen, or sulfur in the ring structure. Exemplary heteroaryl groups include azaindolyl, benzo(b)thienyl, benzimidazolyl, benzofuranyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, benzotriazolyl, benzoxadiazolyl, furanyl, imidazolyl, imidazopyridinyl, indolyl, indolinyl, indazolyl, isoindolinyl, isoxazolyl, isothiazolyl, isoquinolinyl, oxadiazolyl, oxazolyl, purinyl, pyranyl, pyrazinyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrrolyl, pyrrolo[2,3- d]pyrimidinyl, pyrazolo[3,4-d]pyrimidinyl, quinolinyl, quinazolinyl, triazolyl, thiazolyl, thiophenyl, tetrahydroindolyl, tetrazolyl, thiadiazolyl, thienyl, thiomorpholinyl, triazolyl or tropanyl, and the like. The “heteroaryl” may be substituted at one or more ring positions with one or more substituents such as halogen, azide, alkyl, arylalkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aromatic or heteroaromatic moieties, fluoroalkyl (such as trifluromethyl), cyano, or the like. The term “heteroaryl” also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings (the rings are “fused rings”) wherein at least one of the rings is an aromatic group having one or more heteroatoms in the ring structure, e.g., the other cyclic rings may be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and / or heterocyclyls. FH12768200.3 UIX-05025 The term “aralkyl” or “arylalkyl” is a term of art and as used herein refers to an alkyl group substituted with an aryl group, wherein the moiety is appended to the parent molecule through the alkyl group. The term “heteroaralkyl” or “heteroarylalkyl” is a term of art and as used herein refers to an alkyl group substituted with a heteroaryl group, appended to the parent molecular moiety through the alkyl group. The term “alkoxy” as used herein means an alkyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom. Representative examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, 2-propoxy, butoxy, tert-butoxy, pentyloxy, and hexyloxy. The term “alkoxyalkyl” refers to an alkyl group substituted by an alkoxy group. The term “alkoxycarbonyl” means an alkoxy group, as defined herein, appended to the parent molecular moiety through a carbonyl group, represented by -C(=O)-, as defined herein. Representative examples of alkoxycarbonyl include, but are not limited to, methoxycarbonyl, ethoxycarbonyl, and tert-butoxycarbonyl. The term “alkylcarbonyl”, as used herein, means an alkyl group, as defined herein, appended to the parent molecular moiety through a carbonyl group, as defined herein. Representative examples of alkylcarbonyl include, but are not limited to, acetyl, 1-oxopropyl, 2,2- dimethyl-1-oxopropyl, 1-oxobutyl, and 1-oxopentyl. The term “arylcarbonyl”, as used herein, means an aryl group, as defined herein, appended to the parent molecular moiety through a carbonyl group, as defined herein. Representative examples of arylcarbonyl include, but are not limited to, benzoyl and (2-pyridinyl)carbonyl. The term “alkylcarbonyloxy” and “arylcarbonyloxy”, as used herein, means an alkylcarbonyl or arylcarbonyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom. Representative examples of alkylcarbonyloxy include, but are not limited to, acetyloxy, ethylcarbonyloxy, and tert-butylcarbonyloxy. Representative examples of arylcarbonyloxy include, but are not limited to phenylcarbonyloxy. The term “alkenoxy” or “alkenoxyl” means an alkenyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom. Representative examples of alkenoxyl include, but are not limited to, 2-propen-1-oxyl (i.e., CH2=CH-CH2-O-) and vinyloxy (i.e., CH2=CH-O-). FH12768200.3 UIX-05025 The term “aryloxy” as used herein means an aryl group, as defined herein, appended to the parent molecular moiety through an oxygen atom. The term “heteroaryloxy” as used herein means a heteroaryl group, as defined herein, appended to the parent molecular moiety through an oxygen atom. The term “carbocyclyl” as used herein means a monocyclic or multicyclic (e.g., bicyclic, tricyclic, etc.) hydrocarbon radical containing from 3 to 12 carbon atoms that is completely saturated or has one or more unsaturated bonds, and for the avoidance of doubt, the degree of unsaturation does not result in an aromatic ring system (e.g., phenyl). Examples of carbocyclyl groups include 1-cyclopropyl, 1-cyclobutyl, 2-cyclopentyl, 1-cyclopentenyl, 3-cyclohexyl, 1- cyclohexenyl and 2-cyclopentenylmethyl. The term “cyano” is a term of art and as used herein refers to –CN. The term “halo” is a term of art and as used herein refers to –F, –Cl, –Br, or –I. The term “haloalkyl” as used herein refers to an alkyl group, as defined herein, wherein some or all of the hydrogens are replaced with halogen atoms. The term “hydroxy” is a term of art and as used herein refers to –OH. The term “hydroxyalkyl”, as used herein, means at least one hydroxy group, as defined herein, is appended to the parent molecular moiety through an alkyl group, as defined herein. Representative examples of hydroxyalkyl include, but are not limited to, hydroxymethyl, 2- hydroxyethyl, 3-hydroxypropyl, 2,3-dihydroxypentyl, and 2-ethyl-4-hydroxyheptyl. The term “silyl”, as used herein, includes hydrocarbyl derivatives of the silyl (H3Si-) group (i.e., (hydrocarbyl)3Si–), wherein a hydrocarbyl groups are univalent groups formed by removing a hydrogen atom from a hydrocarbon, e.g., ethyl, phenyl. The hydrocarbyl groups can be combinations of differing groups which can be varied in order to provide a number of silyl groups, such as trimethylsilyl (TMS), tert-butyldiphenylsilyl (TBDPS), tert-butyldimethylsilyl (TBS / TBDMS), triisopropylsilyl (TIPS), and [2-(trimethylsilyl)ethoxy]methyl (SEM). The term “silyloxy”, as used herein, means a silyl group, as defined herein, is appended to the parent molecule through an oxygen atom. Certain compounds contained in compositions of the present invention may exist in particular geometric or stereoisomeric forms. In addition, compounds of the present invention may also be optically active. The present invention contemplates all such compounds, including cis- and trans-isomers, (R)- and (S)-enantiomers, diastereoisomers, (D)-isomers, (L)-isomers, the FH12768200.3 UIX-05025 racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention. Additional asymmetric carbon atoms may be present in a substituent such as an alkyl group. All such isomers, as well as mixtures thereof, are intended to be included in this invention. If, for instance, a particular enantiomer of compound of the present invention is desired, it may be prepared by asymmetric synthesis, or by derivation with a chiral auxiliary, where the resulting diastereomeric mixture is separated and the auxiliary group cleaved to provide the pure desired enantiomers. Alternatively, where the molecule contains a basic functional group, such as amino, or an acidic functional group, such as carboxyl, diastereomeric salts are formed with an appropriate optically-active acid or base, followed by resolution of the diastereomers thus formed by fractional crystallization or chromatographic means well known in the art, and subsequent recovery of the pure enantiomers. It will be understood that “substitution” or “substituted with” includes the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., which does not spontaneously undergo transformation such as by rearrangement, fragmentation, decomposition, cyclization, elimination, or other reaction. The term “substituted” is also contemplated to include all permissible substituents of organic compounds. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described herein above. The permissible substituents may be one or more and the same or different for appropriate organic compounds. For purposes of this invention, the heteroatoms such as nitrogen may have hydrogen substituents and / or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms. This invention is not intended to be limited in any manner by the permissible substituents of organic compounds. In certain embodiments, the optional substituents contemplated in this invention include halogen, azide, alkyl, alkenyl, alkynyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, cycloalkyl, (cycloalkyl)alkyl, heterocyclyl, (heterocyclyl)alkyl, hydroxyl, alkoxyl, amino, aminoalkyl, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether (e.g., - alkylene-O(alkyl)), alkylthio, sulfonyl, sulfonamido, ketone (e.g., -CO(alkyl)), aldehyde (- FH12768200.3 UIX-05025 C(O)H), ester (e.g., -COO(alkyl)), haloalkyl, hydroxyalkyl, alkoxyalkyl, haloalkoxy, haloalkoxyalkyl, and cyano. As used herein, the term “optionally substituted” or “substituted or unsubstituted” when it precedes a list of chemical moieties means that the list of chemical moieities that follow are each substituted or unsubstituted. For example, “substituted or unsubstituted aryl, heteroaryl, and cycloalkyl” or “optionally substituted aryl, heteroaryl, and cycloalkyl” means substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted cycloalkyl. The phrase “protecting group”, as used herein, means temporary substituents which protect a potentially reactive functional group from undesired chemical transformations. Examples of such protecting groups include esters of carboxylic acids, silyl ethers of alcohols, and acetals and ketals of aldehydes and ketones, respectively. The field of protecting group chemistry has been reviewed (Greene, T.W.; Wuts, P.G.M. Protective Groups in Organic Synthesis, 2nded.; Wiley: New York, 1991). Protected forms of the inventive compounds are included within the scope of this invention. For purposes of the invention, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 67thEd., 1986- 87, inside cover. Other chemistry terms herein are used according to conventional usage in the art, as exemplified by The McGraw-Hill Dictionary of Chemical Terms (ed. Parker, S., 1985), McGraw- Hill, San Francisco, incorporated herein by reference). Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The term “pharmaceutically acceptable salt” as used herein includes salts derived from inorganic or organic acids including, for example, hydrochloric, hydrobromic, sulfuric, nitric, perchloric, phosphoric, formic, acetic, lactic, maleic, fumaric, succinic, tartaric, glycolic, salicylic, citric, methanesulfonic, benzenesulfonic, benzoic, malonic, trifluoroacetic, trichloroacetic, naphthalene-2-sulfonic, and other acids. Pharmaceutically acceptable salt forms can include forms wherein the ratio of molecules comprising the salt is not 1:1. For example, the salt may comprise more than one inorganic or organic acid molecule per molecule of base, such as two hydrochloric acid molecules per molecule of compound of Formula I. As another example, the salt may FH12768200.3 UIX-05025 comprise less than one inorganic or organic acid molecule per molecule of base, such as two molecules of compound of Formula I per molecule of tartaric acid. The terms “carrier” and “pharmaceutically acceptable carrier” as used herein refer to a diluent, adjuvant, excipient, or vehicle with which a compound is administered or formulated for administration. Non-limiting examples of such pharmaceutically acceptable carriers include liquids, such as water, saline, and oils; and solids, such as gum acacia, gelatin, starch paste, talc, keratin, colloidal silica, urea, and the like. In addition, auxiliary, stabilizing, thickening, lubricating, flavoring, and coloring agents may be used. Other examples of suitable pharmaceutical carriers are described in Remington’s Pharmaceutical Sciences by E.W. Martin, herein incorporated by reference in its entirety. As used herein, the term “oxidizing agent” refers to a reagent that accepts one or more electrons from a substrate. Certain oxidizing agents may also induce the formation of new bonds to oxygen. Illustrative examples of oxidizing agent include, but are not limited to, oxygen, ozone, hydrogen peroxide, periodic acid, sodium periodate, Dess-Martin periodinane, peracetic acid, meta-chloroperbenzoic acid, fluorine, chlorine, bromine, iodine, nitric acid, potassium nitrate, potassium chlorate, peroxydisulfuric acid, peroxymonosulfuric acid, sodium hypochlorite, interhalogen compounds (such as Icl), chromic acids, chromium trioxide, pyridinium chlorochromate, sodium dichromate, potassium permanganate, manganese heptoxide, sodium perborate, nitrous oxide, nitrogen dioxide, dinitrogen tetroxide, ceric ammonium nitrate, and ceric sulfate. As used herein, the term “reducing agent” refers to a reagent that donates one or more electrons to a substrate. Illustrative examples of reducing agents include, but are not limited to, lithium, sodium, potassium, magnesium, aluminum, iron, tin, copper, zinc, sodium hydride, lithium aluminum hydride, sodium borohydride, lithium borohydride, sodium tetraacetoxyborohydride, NaAlH2(OCH2CH2OCH3)2, Na(Hg), Zn(Hg), diborane, nickel boride, sodium dithionate, diisobutylaluminum hydride, and ascorbic acid. EXAMPLES The invention now being generally described, it will be more readily understood by reference to the following examples which are included merely for purposes of illustration of FH12768200.3 UIX-05025 certain aspects and embodiments of the present invention, and are not intended to limit the invention. General Synthetic Methods Reaction mixtures were stirred magnetically. Air- and moisture-sensitive reactions were carried out in flame-dried glassware under nitrogen atmosphere by using standard Schlenk manifold techniques. Fine chemicals were purchased from Acros Organics, Alfa Aesar, Frontier Scientific, Combi-Blocks, or Sigma Aldrich and were used as received unless otherwise mentioned. Anhydrous THF, CH2Cl2, toluene, hexane, acetonitrile and Et2O were dried by passing through a modified Grubbs system of alumina columns, manufactured by Anhydrous Engineering and were transferred under nitrogen via syringe.1H Nuclear Magnetic Resonance (NMR) spectra were recorded in CDCl3at 400 or 500 Mhz on either a Varian Unity 400, Varian Unity 500, Varian Unity Inova 500NB or Bruker 500-MHz spectrometer with broad-band CryoProbe. Chemical shifts (δH) are quoted in parts per million (ppm) and referred to the residual protio solvent signals of CHCl3 (7.27 ppm) or acetone-d6 (2.05 ppm).1H NMR coupling constants are reported in hertz and refer to apparent multiplicities. Data are reported as follows: chemical shift, multiplicity (s = singlet, br. s = broad singlet, d = doublet, t = triplet, q = quartet, quin = quintet, sext = sextet, sept = septet, m = multiplet, dd = doublet of doublet, etc.), coupling constant, integration, and assignment.13C NMR spectra were recorded at 126 MHz. Chemical shifts (δC) are quoted in ppm and referenced to CHCl3(77.0 ppm) or acetone (29.8 ppm).11B NMR spectra were measured at 161 MHz with complete proton decoupling.19F NMR spectra were recorded at 471 MHz. Mass spectra were recorded at the University of Illinois School of Chemical Sciences Mass Spectrometry Laboratory using electron impact ionisation (EI), chemical ionisation (CI) or electrospray ionisation (ESI) techniques for high-resolution mass spectra. HRMS EI and CI were performed on a VG Analytical Autospec mass spectrometer at 70 eV. HRMS ESI was performed on either a Bruker Daltonics Apex IV, 7-Tesla FT-ICR or microTOF II. Example 1: Synthesis of Building Blocks 8-(4-(hydroxymethyl)phenyl)-3,3,4,5,5-pentamethyldihydro-4l4,8l4-[1,3,2]oxazaborolo[2,3- b][1,3,2]oxazaborole-2,6(3H,5H)-dione (3) FH12768200.3 UIX-05025 To a 1 L round bottom flask with a stir bar was added the TIDA ligand (15.0 g, 100 mmol, 1 equiv), 4-(hydroxymethyl) phenylboronic acid 2 (20.0 g, 100 mmol, 1 equiv) and were dissolved in benzene (500 mL) and DMSO (100 mL). The solution was stirred and then the flask was fitted with a Dean-Stark trap and heated to reflux. After refluxing for 6 h, the reaction mixture was cooled to room temperature and then concentrated by rotary evaporation. The resultant DMSO solution was diluted with EtOAc (250 mL) and transferred to a separatory funnel, rinsing the vessel with additional EtOAc. The organic solution was washed with brine (200 mL x 3 to 6 times to ensure complete removal of DMSO), dried over MgSO4, filtered through a cotton plug, and then concentrated by rotary evaporation. The crude concentrate was dissolved in minimal hot acetone with gentle heating and added dropwise by pipette to a vigorously stirred Erlenmeyer flask containing hexanes:Et2O (1:1, 1 L) causing precipitation of the product. Stirring continued until no further precipitation was observed. The product was collected by vacuum filtration through a fine fritted funnel and washed with Et2O (250 mL x 3) to afford a white solid (28.0 g, 88 mmol, 89% yield).1H NMR (500 MHz, CDCl3) δ 7.56 (d, J = 8.1 Hz, 2H), 7.37 (d, J = 7.9 Hz, 2H), 4.59 (s, 2H), 2.49 (s, 3H), 1.85-1.74 (m, 6H), 1.60 – 1.50 (m, 6H).13C NMR (126 MHz, CDCl3) δ 174.82, 142.01, 134.39, 126.54, 65.35, 37.49.11B NMR (161 MHz, CDCl3) δ 9.09. HRMS (ESI+) Calculated for C16H23BNO5(M+H)+: 320.1669, found: 320.1668 4-(3,3,4,5,5-pentamethyl-2,6-dioxotetrahydro-2H-4l4,8l4-[1,3,2]oxazaborolo[2,3- b][1,3,2]oxazaborol-8-yl)benzyl carbonochloridate (1) FH12768200.3 UIX-05025 To an oven dried, septa capped, glass 40 mL vial with a stir bar was added 3 (0.638 g, 2.0 mmol, 1.0 equiv), bis(trichloromethyl) carbonate (BTC, 0.237 g, 0.8 mmol, 0.4 equiv), and acetonitrile (20 mL). The vial was sealed with a teflon septum screw cap and the mixture was stirred for 24 h at 23oC under positive pressure of nitrogen. The reaction mixture was then concentrated by rotary evaporation to afford a white solid. The solid was dissolved in acetone (10 mL) and then added dropwise by pipette to a vigorously stirred Erlenmeyer flask containing hexanes:Et2O (1:1, 150 mL) causing precipitation of the title compound as a white solid (610 mg, 1.6 mmol, 80% yield). Alternatively, the title compound was used directly in reactions with amines without purification, by concentrating the crude reaction mixture to dryness via rotary evaporation and then adding reagents for the following step to the same vessel. Preparation of crystals for X-ray diffraction: To a 5 mL vial was added 10 mg of the title compound. Minimal anhydrous acetone was added to fully dissolve the solid, and then the vial was sealed with a septum cap. A needle was used to pierce the cap and allow slow evaporation of the acetone. The solution was allowed to sit at 23oC until colorless crystals were observed (CCDC 2291420).1H NMR (500 MHz, CDCl3) δ 7.60 (d, J = 8.0 Hz, 2H), 7.37 (d, J = 7.9 Hz, 2H), 5.30 (s, 2H), 2.49 (s, 3H), 1.83-1.73 (m, 6H), 1.63 – 1.44 (m, 6H).13C NMR (126 MHz, CDCl3) δ 174.65, 150.79, 134.57, 134.22, 128.37, 73.40, 37.50.11B NMR (161 MHz, CDCl3) δ 10.24. HRMS (ESI+) Calculated for C17H22BclNO6(M+H)+: 382.1229, found: 382.1219. General Protection Procedure A: Protection of amines with CbzT-Cl To an oven dried glass 40 mL vial with a stir bar CbzT-Cl was added (1.0 mmol, 1.0 equiv) followed by the free amine (1.1 mmol, 1.1 equiv). The vessel was sealed with a septum cap. Using a needle attached to a Schlenk line, the vessel was evacuated and backfilled with nitrogen (3x) and then anhydrous acetonitrile (20 mL) was added by syringe. The mixture was stirred for 16 h at 23oC and was then concentrated by rotary evaporation to afford a solid. To the solid was added EtOAc (30 mL) and then the solution was washed with H2O (30 mL x 3) directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous magnesium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain the crude product FH12768200.3 UIX-05025 mixture. The crude mixture was purified by silica gel column chromatography eluting with 0 to 50% EtOAc / hexanes to yield the CbzT-amine compound. To an oven dried, septa capped, glass 40 mL vial with a stir bar was added S1 (0.241 g, 1.2 mmol, 1.2 equiv), 3 (0.319 g, 1.0 mmol, 1.0 equiv), THF (5 mL), and pyridine (88 μL, 1.1 equiv). The vial was sealed with a Teflon septum screw cap and the mixture was stirred for 4 h at 23oC under positive pressure of nitrogen. After the completion of the reaction, the crude mixture was concentrated by rotary evaporation and then EtOAc (20 mL) was added to the vial. The organic solution was washed with H2O (25 mL x 4), removing water with a pipette after each wash. The organic layer was dried over anhydrous MgSO4, filtered through a cotton plug, and then concentrated via rotary evaporation. The crude product mixture was purified by silica gel (10.0 g) column chromatography eluting with 0 to 50% EtOAc / hexanes to yield the title compound as a white solid (0.387 g, 0.8 mmol, 80% yield).1H NMR (600 MHz, CDCl3) δ 8.28 (d, J = 9.1 Hz, 2H), 7.62 (d, J = 7.6 Hz, 2H), 7.48 – 7.35 (m, 4H), 5.30 (s, 2H), 2.50 (s, 3H), 1.88 – 1.75 (m, 6H), 1.55-1.48 (m, 6H). FH12768200.3 UIX-0502513C NMR (151 MHz, CDCl3) δ 174.67, 155.63, 152.58, 145.56, 135.26, 134.57, 128.04, 125.47, 121.90, 70.92, 37.50.11B NMR (193 MHz, CDCl3) δ 8.91. HRMS (ESI+) Calculated for C23H26BN2O9(M+H)+: 485.1731, found: 485.1727. 4-(3,3,4,5,5-pentamethyl-2,6-dioxotetrahydro-2H-4l4,8l4-[1,3,2]oxazaborolo[2,3- b][1,3,2]oxazaborol-8-yl)benzyl (3-bromophenyl)carbamate (5) Following general procedure A, to an oven dried glass 40 mL vial with a stir bar was added 1 (0.381 g, 1.0 mmol, 1.0 equiv), 4 (0.189 g, 1.1 mmol, 1.1 equiv), and then it was sealed with a septum cap. Using a needle attached to a Schlenk line, the vessel was evacuated and backfilled with nitrogen (3x) and then anhydrous acetonitrile (20 mL) was added by syringe. The mixture was stirred for 16 h at 23 ℃ and was then concentrated by rotary evaporation to afford a solid. To the solid was added EtOAc (30 mL) then the solution was washed with H2O (30 mL x 3) directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous magnesium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain an oil. The oil was purified by silica gel column chromatography eluting with 0 to 50% EtOAc / hexanes to yield the title compound as a white solid (0.464 g, 0.9 mmol, 90% yield). Preparation of crystals for X-ray diffraction: To a 5 mL vial was added 10 mg of the title compound. Minimal anhydrous acetone was added to fully dissolve the solid, and then the vial was sealed with a septum cap. A needle was used to pierce the cap and allow slow evaporation of the acetone. The solution was allowed to sit at 23oC until colorless crystals were observed (CCDC 2290142).1H NMR (600 MHz, CDCl3) δ 7.67 (s, 1H), 7.57 (d, J = 7.8 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 7.23 – 7.12 (m, 2H), 6.73 (s, 1H), 5.20 (s, 2H), 2.48 (s, 3H), 1.95 – 1.71 (m, 6H), 1.59-1.49 (m, 6H). FH12768200.3 UIX-0502513C NMR (151 MHz, CDCl3) δ 174.77, 138.11, 134.43, 130.49, 127.65, 126.67, 122.94, 67.09, 37.51.11B NMR (193 MHz, CDCl3) δ 9.02. HRMS (ESI+) Calculated for C23H27BBrN2O6(M+H)+: 517.1146, found: 517.1149. To an oven dried glass 40 mL vial with a stir bar was added 3-bromoaniline (0.189 g, 1.1 mmol, 1.1 equiv) and S2 (0.484 g, 1.0 mmol, 1.0 equiv), then the vial was sealed with a septum cap. The vessel was evacuated and backfilled with nitrogen (3x) via a needle attached to a Schlenk line. 2.0 M sodium bis(trimethylsilyl)amide in THF solution (0.55 mL, 1.1 mmol, 1.1 equiv) and DMF (5 mL) were added by syringe. The mixture was stirred for 16 h at 23oC. To the solid was added EtOAc (30 mL) then the solution was washed with H2O (30 mL x 3) directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous magnesium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain an oil. The oil was purified by silica gel column chromatography eluting with 50 to 100% EtOAc / hexanes to yield the title compound as a white solid (0.197 g, 0.38 mmol, 38% yield). Characterization data for 5 is the same as above. FH12768200.3 UIX-05025 Following general procedure A, to an oven dried, septa capped, glass 40 mL vial with a stir bar was added 1 (0.381 g, 1.0 mmol, 1.0 equiv), S3 (0.205 g, 1.1 mmol, 1.1 equiv), and then it was sealed with a septum cap. Using a needle attached to a Schlenk line, the vessel was evacuated and backfilled with nitrogen (3x) and then anhydrous acetonitrile (20 mL) was added by syringe. The mixture was stirred for 16 h at 23oC, and then was directly concentrated by rotary evaporation in the same vial to afford a white solid. To the solid was added EtOAc (30 mL) then the solution was washed with H2O (30 mL x 3) directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous magnesium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain an oil. The oil was purified by silica gel column chromatography eluting with 0 to 50% EtOAc / hexanes to yield the title compound as a white solid (0.413 g, 0.78 mmol, 78% yield).1H NMR (600 MHz, CDCl3) δ 7.66 (s, 1H), 7.58 (d, J = 7.7 Hz, 2H), 7.36 (d, J = 7.8 Hz, 2H), 7.19 (d, J = 9.1 Hz, 1H), 7.14 (d, J = 8.2 Hz, 1H), 6.62 (s, 1H), 5.19 (s, 2H), 2.48 (s, 3H), 2.34 (s, 3H), 1.84-1.73 (m, 6H), 1.56-1.49 (m, 6H),13C NMR (151 MHz, CDCl3) δ 174.64, 137.00, 134.29, 130.86, 127.49, 124.93, 66.88, 37.39, 22.17.11B NMR (193 MHz, CDCl3) δ 9.41. HRMS (ESI+) Calculated for C24H29BBrN2O6(M+H)+: 531.1302, found: 531.1302. Use of CbzT-carbonate S2 for preparation of 4-(3,3,4,5,5-pentamethyl-2,6-dioxotetrahydro-2H- 4l4,8l4-[1,3,2]oxazaborolo[2,3-b][1,3,2]oxazaborol-8-yl)benzyl(3-bromo-2- methylphenyl)carbamate (41) FH12768200.3 UIX-05025 To an oven dried glass 40 mL vial with a stir bar was added 3-bromo-4-methylaniline S3 (0.205 g, 1.1 mmol, 1.1 equiv) and S2 (0.484 g, 1.0 mmol, 1.0 equiv), then the vial was sealed with a septum cap. The vessel was evacuated and backfilled with nitrogen (3x) via a needle attached to a Schlenk line. 2.0 M sodium bis(trimethylsilyl)amide in THF solution (0.55 mL, 1.1 mmol, 1.1 equiv) and DMF (5 mL) were added by syringe. The mixture was stirred for 16 h at 23oC. To the solid was added EtOAc (30 mL) then the solution was washed with H2O (30 mL x 3) directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous magnesium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain an oil. The oil was purified by silica gel column chromatography eluting with 50 to 100% EtOAc / hexanes to yield the title compound as a white solid (0.282 g, 0.53 mmol, 53% yield). Characterization data for 41 is the same as above. 4-(3,3,4,5,5-pentamethyl-2,6-dioxotetrahydro-2H-4l4,8l4-[1,3,2]oxazaborolo[2,3- b][1,3,2]oxazaborol-8-yl)benzyl (4-bromopyrimidin-2-yl)carbamate (38) To an oven dried glass 40 mL vial with a stir bar was added 2-amino-4-bromopyrimidine S4 (0.191 g, 1.1 mmol, 1.1 equiv) and S2 (0.484 g, 1.0 mmol, 1.0 equiv), then the vial was sealed with a septum cap. The vessel was evacuated and backfilled with nitrogen (3x) via a needle attached to a Schlenk line. 2.0 M sodium bis(trimethylsilyl)amide in THF solution (0.55 mL, 1.1 mmol, 1.1 equiv) and DMF (5 mL) were added by syringe. The mixture was stirred for 16 h at 23oC. To the solid was added EtOAc (30 mL) then the solution was washed with H2O (30 mL x 3) directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the FH12768200.3 UIX-05025 vial to remove water via pipette in between washes. The organic layer was dried with anhydrous magnesium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain an oil. The oil was purified by silica gel column chromatography eluting with 50 to 100% EtOAc / hexanes to yield the title compound as a white solid (0.31 g, 0.6 mmol, 60% yield). Preparation of crystals for X-ray diffraction: To a 5 mL vial was added 10 mg of the title compound. Minimal anhydrous acetone was added to fully dissolve the solid, and then the vial was sealed with a septum cap. A needle was used to pierce the cap and allow slow evaporation of the acetone. The solution was allowed to sit at 23oC until colorless crystals were observed (CCDC 2291892).1H NMR (151 MHz, CDCl3) δ 8.37 (d, J = 5.2 Hz, 1H), 7.70 (s, 1H), 7.57 (d, J = 7.7 Hz, 2H), 7.39 (d, J = 7.7 Hz, 2H), 7.19 (d, J = 5.2 Hz, 1H), 5.25 (s, 2H), 2.48 (s, 3H), 1.84 – 1.77 (m, 6H), 1.55- 1.48 (s, 6H).13C NMR (151 MHz, CDCl3) δ 174.77, 158.88, 156.99, 153.35, 150.94, 136.58, 134.39, 127.82, 120.49, 67.59, 37.52.11B NMR (161 MHz, CDCl3) δ 9.17. HRMS (ESI+) Calculated for C21H25BBrN4O6(M+H)+: 519.1051, found: 519.1047. Synthesis of the model substrate 4-(5,5,6,7,7-pentamethyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2- yl)benzyl [1,1’-biphenyl]-4-ylcarbamate (8) Following general procedure A, to an oven dried glass 40 mL vial with a stir bar was added 1 (0.381 g, 1.0 mmol, 1.0 equiv) and 4-aminobiphenyl 9 (0.186 g, 1.1 mmol, 1.1 equiv), then it was sealed with a septum cap and evacuated and backfilled with nitrogen (3x) using a needle attached to a Schlenk line. Anhydrous acetonitrile (20 mL) was added by syringe. The mixture was stirred for 16 h at 23oC, then was concentrated by rotary evaporation affording an oil. To oil was added EtOAc (30 mL). The solution was washed with H2O (30 mL x 3) directly in the vial by FH12768200.3 UIX-05025 adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous magnesium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain an oil. The oil was purified by silica gel column chromatography eluting with 0 to 50% EtOAc / hexanes to yield the title compound as a white solid (0.464 g, 0.9 mmol, 90% yield). Preparation of crystals for X-ray diffraction: To a 5 mL vial was added 10 mg of the title compound. Minimal anhydrous acetone was added to fully dissolve the solid, and then the vial was sealed with a septum cap. A needle was used to pierce the cap and allow slow evaporation of the acetone. The solution was allowed to sit at 23oC until colorless crystals were observed (CCDC 2293444).1H NMR (600 MHz, CDCl3) δ 7.64 – 7.52 (m, 6H), 7.49 – 7.37 (m, 6H), 7.32 (m, 1H), 6.75 (br.s, 1H), 5.22 (s, 2H), 2.49 (s, 3H), 1.85-1.72 (s, 6H), 1.60-1.49 (s, 6H).13C NMR (151 MHz, CDCl3) δ 174.65, 140.48, 137.12, 134.29, 128.80, 127.75, 127.53, 127.08, 66.82, 37.39.11B NMR (193 MHz, CDCl3) δ 9.17. HRMS (ESI+) Calculated for C29H32BN2O6(M+H)+: 515.2353, found: 515.2361. Use of CbzT-carbonate S2 for preparation of 4-(5,5,6,7,7-pentamethyl-4,8-dioxo-1,3,6,2- To an oven dried glass 40 mL vial with a stir bar was added 9 [1,1'-biphenyl]-4-amine (0.186 g, 1.1 mmol, 1.1 equiv) and S2 (0.484 g, 1.0 mmol, 1.0 equiv), then the vial was sealed with a septum cap. The vessel was evacuated and backfilled with nitrogen (3x) via a needle attached to a Schlenk line. 2.0 M sodium bis(trimethylsilyl)amide in THF solution (0.55 mL, 1.1 mmol, 1.1 equiv) and DMF (5 mL) were added by syringe. The mixture was stirred for 16 h at 23oC. To the solid was added EtOAc (30 mL) then the solution was washed with H2O (30 mL x 3) FH12768200.3 UIX-05025 directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous magnesium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain an oil. The oil was purified by silica gel column chromatography eluting with 50 to 100% EtOAc / hexanes to yield the title compound as a white solid (0.123 g, 0.24 mmol, 24% yield). Characterization data for 8 is the same as above. To an oven dried glass 40 mL vial with a stir bar was added 4 (0.172 g, 1.0 mmol, 1.0 equiv) and potassium carbonate (0.166 g, 1.2 mmol, 1.2 equiv) in anhydrous THF (10 mL) was added dropwise benzyl chloroformate (0.188 g, 1.1 mmol, 1.1 equiv). The mixture was stirred for 2 h at 0oC to rt under N2. The reaction mixture was concentrated by rotary evaporation affording an oil. To oil was added EtOAc (20 mL). The solution was washed with H2O (20 mL x 3) directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous magnesium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain an oil. The oil was purified by silica gel column chromatography eluting with 0 to 50% EtOAc / hexanes to yield the title compound as a colorless oil (0.275 g, 0.9 mmol, 90% yield).1H NMR (500 MHz, CDCl3) δ 7.64 (br s, 1H), 7.39-7.32 (m, 5H), 7.24-7.12 (m, 3H), 6.72 (br s, 1H), 5.19 (s, 2H).13C NMR (126 MHz, CDCl3) δ 153.01, 139.05, 135.73, 130.28, 128.63, 128.45, 128.32, 126.45, 122.73, 121.51, 117.05, 67.24. HRMS (ESI+) Calculated for C14H13NO2Br (M+H)+: 306.0130, found: 306.0124. FH12768200.3 UIX-05025 To an oven dried glass 40 mL vial with a stir bar 3-bromo-4-methylaniline S3 (0.186 g, 1.0 mmol, 1.0 equiv) was added and potassium carbonate (0.166 g, 1.2 mmol, 1.2 equiv) in anhydrous THF (10 mL) was added dropwise benzyl chloroformate (0.188 g, 1.1 mmol, 1.1 equiv). The mixture was stirred for 2 h at 0oC to rt under N2. The reaction mixture was concentrated by rotary evaporation affording an oil. To oil was added EtOAc (20 mL). The solution was washed with H2O (20 mL x 3) directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous magnesium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain an oil. The oil was purified by silica gel column chromatography eluting with 0 to 50% EtOAc / hexanes to yield the title compound as a colorless oil (0.272 g, 0.85 mmol, 85% yield).1H NMR (500 MHz, CDCl3) δ 7.65 (br s, 1H), 7.41-7.33 (m, 5H), 7.22-7.17 (m, 1H), 7.14 (d, J = 10.0 Hz, 1H), 6.61 (br s, 1H), 5.19 (s, 2H), 2.34 (s, 3H).13C NMR (126 MHz, CDCl3) δ 153.12, 136.52, 135.86, 132.85, 130.80, 128.63, 128.42, 128.32, 124.87, 122.37, 117.60, 67.34, 67.15, 22.12. HRMS (ESI+) Calculated for C15H15NO2Br (M+H)+: 320.0286 , found: 320.0280. Synthesis of Benzyl (4-bromopyrimidin-2-yl)carbamate (S8) To an oven dried glass 40 mL vial with a stir bar 4-bromopyrimidin-2-amine (0.169 g, 1.0 mmol, 1.0 equiv) was added and benzyl (4-nitrophenyl) carbonate (0.328 g, 1.2 mmol, 1.2 equiv) in anhydrous dichloromethane (10 mL) was added dropwise pyridine (0.160 g, 2.0 mmol, 2.0 equiv). The mixture was stirred for 2 h at 0oC to rt under N2. The reaction mixture was concentrated by rotary evaporation affording an oil. To oil was added EtOAc (20 mL). The solution was washed with H2O (20 mL x 3) directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous magnesium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain an oil. The oil was purified by silica gel column FH12768200.3 UIX-05025 chromatography eluting with 0 to 50% EtOAc / hexanes to yield the title compound as a colorless oil (0.188 g, 0.61 mmol, 61% yield).1H NMR (500 MHz, CDCl3) δ 8.34 (d, J = 10.0 Hz, 1H), 7.98 (br s, 1H), 7.45-7.31 (m, 5H), 7.17 (d, J = 10.0 Hz, 1H), 5.25 (s, 2H).13C NMR (126 MHz, CDCl3) δ 158.65, 156.89, 153.21, 150.81, 135.31, 128.63, 128.56, 128.54, 120.23, 67.71. HRMS (ESI+) Calculated for C12H11N3O2Br (M+H)+: 308.0035, found: 308.0035. To an oven dried glass 40 mL vial with a stir bar was added 9 (0.169 g, 1.0 mmol, 1.0 equiv) and potassium carbonate (0.166 g, 1.2 mmol, 1.2 equiv) in anhydrous THF (10 mL) was added dropwise benzyl chloroformate (0.188 g, 1.1 mmol, 1.1 equiv). The mixture was stirred for 2 h at 0oC to rt under N2. The reaction mixture was concentrated by rotary evaporation affording an oil. To oil was added EtOAc (20 mL). The solution was washed with H2O (20 mL x 3) directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous magnesium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain an oil. The oil was purified by silica gel column chromatography eluting with 0 to 50% EtOAc / hexanes to yield the title compound as a colorless oil (0.261 g, 0.86 mmol, 86% yield).1H NMR (500 MHz, CDCl3) δ 7.60-7.52 (m, 4H), 7.50-7.30 (m, 10H), 6.71 (br s, 1H), 5.23 (s, 2H).13C NMR (126 MHz, CDCl3) δ 153.25, 140.48, 137.04, 136.46, 135.98, 128.75, 128.64, 128.40, 128.35, 127.71, 127.02, 126.79, 118.93, 67.11. HRMS (ESI+) Calculated for C20H18NO2(M+H)+: 304.1338, found: 304.1332. Synthesis of Benzyl (3-(m-tolylamino)phenyl)carbamate (S10) FH12768200.3 UIX-05025 In an argon filled glovebox, an oven dried glass 40 mL vial with a stir bar was added S6 (0.305 g, 1.0 mmol, 1.0 equiv), 6 (0.139 g, 1.3 mmol, 1.3 equiv), tBuXPhos-Pd-G3 (0.159 g, 0.2 mmol, 0.2 equiv), tBuXPhos (0.064 g, 0.15 mmol, 0.15 equiv) and TMSOK (257 mg, 2.0 mmol, 2 equiv). The vial was sealed with a PTFE septum cap. The vial was placed under positive pressure of argon via a needle attached to a Schlenk line, and then anhydrous, argon-sparged THF (10 mL) was added, and the reaction was stirred at 23 ˚C for 1 h. The reaction mixture was diluted with EtOAc (30 mL) and filtered through a silica plug, washing with additional EtOAc (50 mL). The EtOAc eluent was concentrated via rotary evaporation to obtain an oil. The oil was purified by silica gel column chromatography eluting with 0 to 50% EtOAc / hexanes to yield the title compound as a colorless oil (0.232 g, 0.70 mmol, 70% yield).1H NMR (500 MHz, CDCl3) δ 7.42-7.32 (m, 5H), 7.17-7.14 (m, 3H), 6.93-6.88 (m, 2H), 6.85 (d, J = 10.0 Hz, 1H), 6.78 (d, J = 10.0 Hz, 2H), 6.62 (br s, 1H), 5.69 (br s, 1H), 5.19 (s, 2H), 2.32 (s, 3H).13C NMR (126 MHz, CDCl3) δ 144.33, 142.54, 139.26, 138.84, 136.07, 129.85, 129.19, 128.64, 128.38, 128.34, 122.36, 119.24, 115.60, 112.29, 67.02, 21.53. HRMS (ESI+) Calculated for C21H21N2O2(M+H)+: 333.1603, found: 333.1608. Synthesis of (4-((((6-bromonaphthalen-2-yl)carbamoyl)oxy)methyl)phenyl)boronic acid TIDA ester (21) Following general procedure A, to an oven dried glass 40 mL vial with a stir bar was added 1 (0.598 g, 1.73 mmol, 1.0 equiv), S5 (0.383g, 1.57 mmol, 1.1 equiv), and then it was sealed with a septum cap. Using a needle attached to a Schlenk line, the vessel was evacuated and backfilled with nitrogen (3x) and then anhydrous acetonitrile (18 mL) was added by syringe. The mixture was stirred for 16 h at 23oC and was then concentrated by rotary evaporation to afford a solid. To FH12768200.3 UIX-05025 the solid was added EtOAc (30 mL) then the solution was washed with H2O (30 mL x 3) in a separatory funnel, shaking rigorously, and then removing water in between washes. The organic layer was dried with anhydrous magnesium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain a pink solid. The pink solid was purified by silica gel column chromatography eluting with 0 to 100% EtOAc / hexanes to yield the title compound as a white solid (0.660 g, 1.16mmol, 74% yield).1H NMR (600 MHz, CDCl3) δ 8.00 (s, 1H), 7.93 (d, J=1.9Hz, 1H), 7.69 (d, J = 8.8 Hz, 1H), 7.64 (d, J=8.8, 1H), 7.59 (d, J=7.6, 2H), 7.52 (dd, J1=1.94Hz, J2=8.7Hz, 1H), 7.41-7.37 (m, 3H), 6.85 (s, 1H), 5.24 (s,2H), 2.49 (s, 3H), 1.80 (s, 6H), 1.54 (s, 6H).13C NMR (151 MHz, CDCl3) δ 174.60, 136.99, 135.61, 134.32, 132.41, 131.23, 129.98, 129.62, 129.08, 128.06, 127.54, 118.48, 66.96, 37.38. HRMS (ESI+) Calculated for C27H28BBrN2O6 (M+H)+: 566.1224, found: 567.1132. Following general procedure A, to an oven dried glass 40 mL vial with a stir bar was added 1 (1.20 g, 3.14 mmol, 1.0 equiv), S11 (741 mg, 3.46 mmol, 1.1 equiv), and then it was sealed with a septum cap. Using a needle attached to a Schlenk line, the vessel was evacuated and backfilled with nitrogen (3x) and then anhydrous acetonitrile (20 mL) was added by syringe. The mixture was stirred for 16 h at 23oC and was then concentrated by rotary evaporation to afford a solid. To the solid was added EtOAc (30 mL) then the solution was washed with H2O (30 mL x 3) directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous magnesium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain a pink solid. The pink solid was purified by silica gel column chromatography eluting with FH12768200.3 UIX-05025 0 to 100% EtOAc / hexanes to yield the title compound as a white solid (1.07 g, 1.91 mmol, 61% yield).1H NMR (500 MHz, CDCl3) δ 7.6 (d, J = 7.6 Hz, 2H), 7.5 (s, 1H), 7.4 (d, J = 7.8 Hz, 2H), 7.1 (s, 1H), 7.1 (t, J = 1.6 Hz, 1H), 6.7 (s, 1H), 5.2 (s, 2H), 3.0 – 2.7 (septet, 1H), 2.5 (s, 3H), 1.8 (s, 6H), 1.6 – 1.5 (s, 6H), 1.2 (d, J = 6.8 Hz, 6H).13C NMR (126 MHz, CDCl3) δ 174.7, 153.1, 151.9, 139.0, 137.0, 134.4, 134.2, 127.4, 124.7, 122.6, 119.0, 115.5, 66.8, 46.1, 37.4, 34.1, 30.9, 23.7. HRMS (ESI+) Calculated for (M+H)+: 559.1615 , found: 559.1459. Free Amine vs. CBzT-amine coupling In an argon-filled glovebox, 5 (200 mg, 0.386 mmol, 1.0 equiv), 15 (169 mg, 0.773 mmol, 2.0 equiv), Pd-P(tBu)3-G4 (44 mg, 0.078 mmol, 0.2 equiv), and TMSOK (99 mg, 0.78 mmol, 2.0 equiv) were added to an oven dried 20 mL vial equipped with a stir bar. The vial was sealed with a PTFE septum cap, removed from the glovebox, and placed under positive N2pressure via a needle attached to a Schlenk line. Anhydrous THF (5 mL) was added and the reaction was stirred at 45 ˚C for 10 minutes. HPLC-MS analysis showed clean conversion to the desired product with minimal remaining starting materials 5 and 15. FH12768200.3 UIX-05025 In an argon-filled glovebox, 4 (200 mg, 1.16 mmol, 1.0 equiv), 15 (211.9 mg, 2.33 mmol, 2.0 equiv), Pd-P(tBu)3-G4 (135.9 mg, 0.232 mmol, 0.2 equiv), and TMSOK (298.3 mg, 2.33 mol, 2.0 equiv) were added to an oven dried 20 mL vial equipped with a stir bar. The vial was sealed with a PTFE septum cap, removed from the glovebox, and placed under positive N2pressure via a needle attached to a Schlenk line. Anhydrous THF (5 mL) was added and the reaction was stirred at 45 ˚C for 10 minutes. HPLC-MS analysis showed minimal conversion to the desired product, remaining starting materials 15 and 4, and numerous unidentified side products. Example 2: Deprotection Conditions for CBzT The influence of various reaction conditions on the deprotection yield of 9 is shown below. General Deprotection Procedure A To a 20 mL vial with a stir bar the CbzT-amine was added (0.037 mmol, 1.0 equiv) followed by NaBH4(37 mg, 10.0 equiv, 0.97 mmol) and 10% palladium on carbon (2 mg, 0.2 equiv). The vial was sealed with a septum cap and then evacuated and backfilled with nitrogen (3x) using a needle attached to a Schlenk line. MeOH (3 mL) was added by syringe and then an empty balloon attached to a syringe fitted with a needle was placed through the septum to minimize FH12768200.3 UIX-05025 the buildup of pressure while preventing loss of generated hydrogen. The reaction was stirred at 65 ˚C for 7 hours. The reaction mixture was concentrated by rotary evaporation. Hexanes (30 mL) was added, and the solution was filtered through a silica plug rinsing with additional hexanes (100 mL). The hexanes layer was discarded, and the silica plug was flushed with Et2O (100 mL). The Et2O solution was concentrated via rotary evaporation to yield the title compound. General Deprotection Procedure B To a 40 mL vial with a stir bar the CbzT-amine wes added ( 0.064 mmol, 1 equiv) and then THF (5 mL) was added by syringe. The solution was vigorously stirred and then 3 M aqueous LiOH* (300 μL, 1.3 mmol, 15 equiv) was added by syringe. Aqueous 30% H2O2 (200 μL) was added by syringe, the vial was sealed tightly with a PTFE septum cap, the vial was placed in a pre- equilibrated 55 ˚C heating block, and then the reaction was stirred for 12 hours. Then hexanes was added (30 mL) and filtered through a silica plug rinsing with additional hexanes (100 mL), Et2O (100 mL) and EtOAc (100 mL) and then the eluents were discarded. The silica plug was washed with acetone (250 mL) to elute the product. The acetone solution was concentrated via rotary evaporation and to give the desired product each time. Optimization of CBzT deprotection procedures FH12768200.3 UIX-05025 Deprotection of 8 BF3OEt2with to prepare [1,1'-biphenyl]-4-amine (9) To a 20 mL vial with a stir bar was added 8 (51 mg, 0.1 mmol, 1.0 equiv) in CH2Cl2(5.0 mL), and then the vial was sealed with a septum cap. 1.0 M EtSH (0.18 g, 2.9 mmol, 29 equiv) and BF3OEt2(0.145 g, 1.0 mmol, 10 equiv) were added by syringe. The mixture was stirred for 14 h at 23oC. No desired product was observed. FH12768200.3 UIX-05025 To a 20 mL vial with a stir bar was added 8 (51 mg, 0.1 mmol, 1.0 equiv), and then the vial was sealed with a septum cap.1.0 M tetrabutylammonium fluoride in THF solution (0.12 mL, 0.12 mmol, 1.2 equiv), and THF (2 mL) were added by syringe. The mixture was stirred for 16 h at 60oC. After cooling, the mixture was concentrated by rotary evaporation affording a mixture solid. The solution was washed with H2O (5 mL x 3) directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous sodium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain an oil. The oil was diluted with hexanes (30 mL) and filtered through a silica plug. The hexane was then discarded, and the silica plug was eluted with Et2O (100 mL). The Et2O eluent was then concentrated via rotary evaporation to yield the title compound as a light brown solid (15 mg, 0.9 mmol, 65% yield).1H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 7.7 Hz, 2H), 7.49 – 7.35 (m, 3H), 7.26 (d, J = 9.1 Hz, 2H), 6.76 (d, J = 6.8 Hz, 2H), 3.73 (br. s., 2H). To a 20 mL vial with a stir bar was added 8 (51 mg, 0.1 mmol, 1.0 equiv) and trimethylsilyl iodide (28 μl, 0.2 mmol, 2 equiv) and acetonitrile (10 mL), then it was sealed with a septum cap. The mixture was stirred for 2 h at 23oC and then concentrated by rotary evaporation to afford a solid. To the oil was added EtOAc (10 mL). The solution was washed with H2O (5 mL x 3) directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous sodium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain an oil. The oil was diluted with hexanes (30 mL) and filtered through a silica plug. The hexane eluent was discarded, and the silica plug was washed with Et2O (100 mL). The Et2O eluent was then concentrated via rotary evaporation to yield the title compound as a light brown solid (15 mg, 0.9 mmol, 90% yield). FH12768200.3 UIX-05025 To a 20 mL vial with a stir bar was added 8 (51 mg, 0.1 mmol, 1.0 equiv) and trimethylsilyl iodide (28 μl, 0.2 mmol, 2 equiv) and acetonitrile (10 mL), then it was sealed with a septum cap. The mixture was stirred for 1 h at 82oC and then concentrated by rotary evaporation to afford a solid. To the oil was added EtOAc (10 mL). The solution was washed with H2O (5 mL x 3) directly in the vial by adding water, sealing of the vial, shaking rigorously, and then opening the vial to remove water via pipette in between washes. The organic layer was dried with anhydrous sodium sulfate, filtered through a cotton plug, and then concentrated by rotary evaporation to obtain an oil. The oil was diluted with hexanes (30 mL) and filtered through a silica plug. The hexane eluent was discarded, and the silica plug was washed with Et2O (100 mL). The Et2O eluent was then concentrated via rotary evaporation to yield the title compound as a light brown solid (15 mg, 0.09 mmol, 90% yield). To a 20 mL vial with a stir bar was added 8 (20 mg, 0.037 mmol, 1.0 equiv) and 10 wt % of 10% Pd / C (2 mg, 0.2 equiv). The vial was sealed with a septum cap and was then evacuated and backfilled with nitrogen (3x) using a needle attached to a Schlenk line. MeOH (3 mL) was added by syringe and then an empty (deflated) balloon attached to a syringe fitted with a needle was placed through the septum to avoid the buildup of pressure while preventing loss of generated hydrogen. The reaction was stirred at 23 ˚C for 14 hours. After the reaction was completed, the solvent was removed by vacuum. Purification of the residue was conducted via FH12768200.3 UIX-05025 flashchromatography and afforded the desired product as light brown solid (15 mg, 0.089 mmol, 90%). Following general deprotection procedure A, to a 20 mL vial with a stir bar was added 8 (20 mg, 0.037 mmol, 1.0 equiv), NaBH4 (111 mg, 30.0 equiv, 2.91 mmol) and 10 wt % of 10% Pd / C (2 mg). The vial was sealed with a septum cap and was then evacuated and backfilled with nitrogen (3x) using a needle attached to a Schlenk line. MeOH (3 mL) was added by syringe and then an empty (deflated) balloon attached to a syringe fitted with a needle was placed through the septum to avoid the buildup of pressure while preventing loss of generated hydrogen. The reaction was stirred at 65 ˚C for 7 hours. The reaction mixture was concentrated by rotary evaporation and was then diluted with hexanes (30 mL) and filtered through a silica plug. The hexanes layer was discarded, and the silica plug was flushed with Et2O (100 mL). The Et2O eluent solution was concentrated via rotary evaporation to yield the title compound as a light brown solid (5.7 mg, 0.034 mmol, 91% yield). Following general deprotection procedure A, to a 20 mL vial with a stir bar was added 7 (20 mg, 0.036 mmol, 1.0 equiv), NaBH4 (111 mg, 30.0 equiv, 2.91 mmol) and 10 wt % of 10% Pd / C (2 mg). The vial was sealed with a septum cap and was then evacuated and backfilled with nitrogen (3x) using a needle attached to a Schlenk line. MeOH (3 mL) was added by syringe and then an empty (deflated) balloon attached to a syringe fitted with a needle was placed through the septum to avoid the buildup of pressure while preventing loss of generated hydrogen. The reaction was FH12768200.3 UIX-05025 stirred at 65 ˚C for 7 hours. The reaction mixture was concentrated by rotary evaporation and was then diluted with hexanes (30 mL) and filtered through a silica plug. The hexanes layer was discarded, and the silica plug was flushed with Et2O (100 mL). The Et2O eluent solution was concentrated via rotary evaporation to yield the title compound as a light brown solid (6.4 mg, 0.032 mmol, 90% yield).1H NMR (600 MHz, CDCl3) δ 7.15 (dd, J = 8.6, 7.5 Hz, 1H), 7.04 (t, J = 7.9 Hz, 1H), 6.92 – 6.83 (m, 2H), 6.75 (d, J = 7.5 Hz, 1H), 6.46 (ddd, J = 7.9, 2.1, 0.9 Hz, 1H), 6.42 (t, J = 2.1 Hz, 1H), 6.27 (ddd, J = 7.9, 2.1, 0.9 Hz, 1H), 5.57 (s, 1H), 3.62 (br. s, 2H), 2.31 (s, 3H).13C NMR (151 MHz, CDCl3) δ 147.61, 144.59, 143.11, 139.29, 130.31, 129.24, 122.03, 119.14, 115.57, 108.52, 108.10, 104.15, 21.67. HRMS (ESI+) Calculated for C13H15N2(M+H)+: 199.1235, found: 199.1234. Deprotection of 8 to prepare [1,1'-biphenyl]-4-amine (9) To a 20 mL vial with a stir bar was added 8 (20 mg, 0.037 mmol, 1.0 equiv), NaBH4(37 mg, 10.0 equiv, 0.97 mmol) and 10 wt % of 10% Pd / C (2 mg). The vial was sealed with a septum cap and was then evacuated and backfilled with nitrogen (3x) using a needle attached to a Schlenk line. MeOH (3 mL) was added by syringe and then an empty (deflated) balloon attached to a syringe fitted with a needle was placed through the septum to avoid the buildup of pressure while preventing loss of generated hydrogen. The reaction was stirred at 23 ˚C for 2 hours. The reaction mixture was concentrated by rotary evaporation and was then diluted with hexanes (30 mL) and filtered through a silica plug. The hexanes layer was discarded, and the silica plug was flushed with Et2O (100 mL). The Et2O eluent solution was concentrated via rotary evaporation to yield the title compound as a light brown solid (6.1 mg, 93 % yield). Deprotection of 7 to prepare [1,1'-biphenyl]-4-amine (12) FH12768200.3 UIX-05025 To a 20 mL vial with a stir bar was added 7 (100 mg, 0.184 mmol, 1.0 equiv), NaBH4(70 mg, 10.0 equiv, 1.84 mmol) and 10 wt % of 10% Pd / C (10 mg, 0.1 equiv). The vial was sealed with a septum cap and was then evacuated and backfilled with nitrogen (3x) using a needle attached to a Schlenk line. MeOH (5 mL) was added by syringe and then an empty (deflated) balloon attached to a syringe fitted with a needle was placed through the septum to avoid the buildup ofpressure while preventing loss of generated hydrogen. The reaction was stirred at 23̊ C for 2 hours.The reaction mixture was concentrated by rotary evaporation and was then diluted with hexanes (30 mL) and filtered through a silica plug. The hexanes layer was discarded, and the silica plug was flushed with Et2O (100 mL). The Et2O eluent solution was concentrated via rotary evaporation to yield the title compound as a light brown solid (34 mg, 91 % yield).1H NMR (600 MHz, CDCl3) δ 7.15 (dd, J = 8.6, 7.5 Hz, 1H), 7.04 (t, J = 7.9 Hz, 1H), 6.92 – 6.83 (m, 2H), 6.75 (d, J = 7.5 Hz, 1H), 6.46 (ddd, J = 7.9, 2.1, 0.9 Hz, 1H), 6.42 (t, J = 2.1 Hz, 1H), 6.27 (ddd, J = 7.9, 2.1, 0.9 Hz, 1H), 5.57 (s, 1H), 3.62 (br. s, 2H), 2.31 (s, 3H).13C NMR (151 MHz, CDCl3) δ 147.61, 144.59, 143.11, 139.29, 130.31, 129.24, 122.03, 119.14, 115.57, 108.52, 108.10, 104.15, 21.67. HRMS (ESI+) Calculated for C13H15N2(M+H)+: 199.1235, found: 199.1234. Following general deprotection procedure B, to a 40 mL vial with a stir bar was added 8 (33 mg, 0.064 mmol, 1 equiv) and then THF (5 mL) was added by syringe. The solution was vigorously stirred and then 3 M aqueous LiOH* (300 μL, 1.3 mmol, 15 equiv) was added by syringe. Aqueous 30% H2O2 (200 μL) was added by syringe, the vial was sealed tightly with a PTFE septum cap, the vial was placed in a pre-equilibrated 55 ˚C heating block, and then the reaction was stirred for FH12768200.3 UIX-05025 12hours. The reaction mixture was concentrated by rotary evaporation and was then diluted with hexanes (30 mL) and filtered through a silica plug. The hexanes layer was discarded, and the silica plug was flushed with Et2O (100 mL). The Et2O eluent solution was concentrated via rotary evaporation to yield the title compound as a light brown solid (7.4 mg, 0.044 mmol, 68% yield). Following general deprotection procedure B, to a 40 mL vial with a stir bar was added 7 (35 mg, 0.064 mmol, 1 equiv) and then THF (5 mL) was added by syringe. The solution was vigorously stirred and then 3 M aqueous LiOH* (300 μL, 1.3 mmol, 15 equiv) was added by syringe. Aqueous 30% H2O2 (200 μL) was added by syringe, the vial was sealed tightly with a PTFE septum cap, the vial was placed in a pre-equilibrated 55 ˚C heating block, and then the reaction was stirred for 12hours. The reaction mixture was concentrated by rotary evaporation and was then diluted with hexanes (30 mL) and filtered through a silica plug. The hexanes layer was discarded, and the silica plug was flushed with Et2O (100 mL). The Et2O eluent solution was concentrated via rotary evaporation to yield the title compound as a light brown solid (8.7 mg, 0.044 mmol, 68% yield). Example 3: Manual Synthesis of Oligomers FH12768200.3 UIX-05025 In an argon filled glovebox, an oven dried 40 mL vial equipped with a stir bar was charged with 5 (300 mg, 0.580 mmol, 1 equiv), 6 (80 mg, 0.75 mmol, 1.3 equiv), tBuXPhos-Pd-G3 (92 mg, 0.11 mmol, 0.2 equiv), tBuXPhos (37 mg, 0.09 mmol, 0.15 equiv) and TMSOK (150 mg, 1.15 mmol, 2 equiv). The vial was sealed with a PTFE septum cap. The vial was placed under positive pressure of argon via a needle attached to a Schlenk line, and then anhydrous, argon- sparged THF (5 mL) was added and the reaction was stirred at 23 ˚C for 60 minutes. The reaction mixture was diluted with hexane (30 mL) and the solution was filtered through a silica plug, washing with additional hexanes (100 mL). The silica plug was then washed with Et2O (250 mL). The hexanes and Et2O eluents were discarded and then the silica plug was washed with EtOAc (250 mL). The EtOAc eluent was concentrated via rotary evaporation to yield the title compound as light brown solid (220 mg, 70% yield).1H NMR (600 MHz, CDCl3) δ 7.55 (d, J = 7.5 Hz, 2H), 7.35 (d, J = 7.4 Hz, 2H), 7.19 – 7.12 (m, 3H), 6.89 (d, J = 8.6 Hz, 2H), 6.85 (m, J = 8.1 Hz, 1H), 6.77 (t, J = 6.4 Hz, 2H), 6.72 (s, 1H), 5.71 (br. s, 1H) 5.18 (s, 2H), 2.46 (s, 3H), 2.31 (s, 3H), 1.78 (s, 6H), 1.52 (s, 6H).13C NMR (151 MHz, CDCl3) δ 174.80, 144.44, 142.63, 139.38, 134.35, 129.97, 129.30, 127.62, 122.46, 119.33, 115.67, 112.37, 66.79, 37.48, 21.65.11B NMR (161 MHz, CDCl3) δ 10.87. HRMS (ESI+) Calculated for C21H25BBrN4O6(M+H)+: 519.1051, found: 519.1047. To a 20 mL vial with a stir bar was added 7 (100 mg, 0.184 mmol, 1.0 equiv), NaBH4(70 mg, 10.0 equiv, 1.84 mmol) and 10 wt % of 10% Pd / C (10 mg, 0.1 equiv). The vial was sealed FH12768200.3 UIX-05025 with a septum cap and was then evacuated and backfilled with nitrogen (3x) using a needle attached to a Schlenk line. MeOH (5 mL) was added by syringe and then an empty (deflated) balloon attached to a syringe fitted with a needle was placed through the septum to avoid the buildup ofpressure while preventing loss of generated hydrogen. The reaction was stirred at 23̊ C for 2 hours.The reaction mixture was concentrated by rotary evaporation and was then diluted with hexanes (30 mL) and filtered through a silica plug. The hexanes layer was discarded, and the silica plug was flushed with Et2O (100 mL). The Et2O eluent solution was concentrated via rotary evaporation to yield the title compound as a light brown solid (34 mg, 91 % yield).1H NMR (600 MHz, CDCl3) δ 7.15 (dd, J = 8.6, 7.5 Hz, 1H), 7.04 (t, J = 7.9 Hz, 1H), 6.92 – 6.83 (m, 2H), 6.75 (d, J = 7.5 Hz, 1H), 6.46 (ddd, J = 7.9, 2.1, 0.9 Hz, 1H), 6.42 (t, J = 2.1 Hz, 1H), 6.27 (ddd, J = 7.9, 2.1, 0.9 Hz, 1H), 5.57 (s, 1H), 3.62 (br. s, 2H), 2.31 (s, 3H).13C NMR (151 MHz, CDCl3) δ 147.61, 144.59, 143.11, 139.29, 130.31, 129.24, 122.03, 119.14, 115.57, 108.52, 108.10, 104.15, 21.67. HRMS (ESI+) Calculated for C13H15N2(M+H)+: 199.1235, found: 199.1234. Preparation of N-(3-(m-tolylamino)phenyl)benzamide (14) An oven dried 40 mL vial equipped with a stir bar was charged with the benzoic acid 13 (10 mg, 0.81 mmol, 1.0 equiv) and then the vial was sealed with a PTFE septum cap. The vial was evacuated and backfilled with nitrogen (3x) via a needle attached to a Schlenk line and then a mixture of pyridine:EtOAc (2:1, 2 mL) was added by syringe. The solution was stirred vigorously, then T3P (50 wt% in EtOAc, 0.163mmol, 2 equiv) was added dropwise by syringe, resulting in a homogeneous yellow solution. The reaction mixture was stirred at room temperature for 15 hours. EtOAc (5 mL) was added to the reaction mixture and then the organic solution was washed with water (5 mL x 3) directly in the vial using a syringe to remove aqueous layers after each wash. The solution was washed with brine (5 mL). The organic layer was dried over anhydrous sodium sulfate, filtered through a cotton plug, and then concentrated via rotary evaporation. The crude FH12768200.3 UIX-05025 mixture was purified via silica gel column chromatography (0 to 100% hexanes / EtOAc) to yield the title compound as a light brown solid (11 mg, 0.36 mmol, 45% yield).1H NMR (600 MHz, CDCl3) δ 8.01 – 7.70 (m, 2H), 7.76 (s, 1H), 7.57 – 7.53 (m, 1H), 7.52 – 7.42 (m, 3H), 7.23 (t, J = 8.0 Hz, 1H), 7.18 (t, J = 7.7 Hz, 1H), 7.07 (dd, J = 8.0, 2.0 Hz, 1H), 6.98 – 6.92 (m, 2H), 6.91 – 6.85 (m, 1H), 6.79 (d, J = 7.5 Hz, 1H), 5.76 (s, 1H), 2.32 (s, 3H).13C NMR (151 MHz, CDCl3) δ 165.84, 144.51, 142.62, 139.44, 139.10, 135.21, 131.99, 129.99, 129.35, 128.95, 127.14, 122.59, 119.52, 115.84, 113.35, 112.28, 109.11, 21.68. HRMS (ESI+) Calculated for C20H19N2O (M+H)+: 303.1497, found: 303.1495. In an argon-filled glovebox, 5 (200 mg, 0.386 mmol, 1 equiv), 15 (169 mg, 0.773 mmol, 2 equiv), Pd-P(tBu)3-G4 (44 mg, 0.078 mmol, 0.2 equiv), and TMSOK (99 mg, 0.78 mmol, 2 equiv) were added to a 20 mL vial. The vial was sealed with a PTFE septum cap, removed from the glovebox, and placed under positive argon pressure via a needle attached to a Schlenk line. Anhydrous, argon-sparged THF (5 mL) was added and the reaction was stirred at 23 ˚C for 10 minutes. The reaction mixture was diluted with hexane (30 mL) and filtered through a silica plug. The silica plug was washed with additional hexanes (250 mL) and the hexane eluent was discarded. The silica plug was washed with Et2O (250 mL) and then the solution was concentrated via rotary evaporation to yield 16 as a white solid (191 mg, 93% yield). FH12768200.3 UIX-050251H NMR (600 MHz, CDCl3) δ 7.65 (d, J = 13.8 Hz, 1H), 7.58 (d, J = 7.6 Hz, 2H), 7.40 – 7.24 (m, 6H), 7.33 – 7.27 (m, 2H), 7.16 (d, J = 7.4 Hz, 1H), 6.79 (br. s, 1H), 5.22 (s, 2H), 2.48 (s, 3H), 2.41 (s, 3H), 1.79 (s, 6H), 1.60 (s, 6H).13C NMR (151 MHz, CDCl3) δ 174.66, 142.42, 140.66, 137.16, 134.28, 129.43, 128.68, 128.30, 127.47, 124.30, 122.48, 66.75, 37.39, 21.55.11B NMR (161 MHz, CDCl3) δ 9.03. HRMS (ESI+) Calculated for C30H34BN2O6(M+H)+: 529.2510, found: 529.2510. To a 20 mL vial with a stir bar was added 16 (50 mg, 0.095 mmol, 1.0 equiv), NaBH4(35 mg, 10.0 equiv, 0.95 mmol) and 10 wt % of 10% Pd / C (5 mg, 0.1 equiv). The vial was sealed with a septum cap and was then evacuated and backfilled with nitrogen (3x) using a needle attached to a Schlenk line. MeOH (3 mL) was added by syringe and then an empty (deflated) balloon attached to a syringe fitted with a needle was placed through the septum to avoid the buildup of pressure while preventing loss of generated hydrogen. The reaction was stirred at 23 ˚C for 2 hours. The reaction mixture was concentrated by rotary evaporation and was then diluted with hexanes (30 mL) and filtered through a silica plug. The hexanes layer was discarded, and the silica plug was flushed with Et2O (100 mL). The Et2O eluent solution was concentrated via rotary evaporation to yield the title compound as a light brown solid (15 mg, 90 % yield).1H NMR (600 MHz, CDCl3) δ 7.43 – 7.38 (m, 2H), 7.35 (t, J = 7.5 Hz, 1H), 7.28 – 7.24 (m, 1H), 7.19 (d, J = 7.5 Hz, 1H), 7.03 (dt, J = 7.7, 1.4 Hz, 1H), 6.95 (q, J = 1.7 Hz, 1H), 6.72 (d, J = 7.9 Hz, 1H), 3.88 (br. s, 3H), 2.45 (s, 3H).13C NMR (151 MHz, CDCl3) δ 146.58, 142.73, 141.48, 138.32, 129.76, 128.68, 128.11, 128.06, 124.35, 118.00, 114.25, 114.18, 21.68. HRMS (ESI+) Calculated for C13H14N (M+H)+: 184.1126, found: 184.1120. FH12768200.3 UIX-05025 In an argon filled glovebox, an oven dried 40 mL vial equipped with a stir bar was charged with 17 (20 mg, 0.109 mmol, 1 equiv), 18 (23 mg, 0.141 mmol, 1.3 equiv), Pd(OAc)2(2.5 mg, 0.01 mmol, 0.1 equiv), SPhos (9 mg, 0.02 mmol, 0.2 equiv) and Cs2CO3(50 mg, 0.15 mmol, 1.4 equiv). The vial was sealed with a PTFE septum cap, removed from the glovebox, and placed under positive pressure of argon via a needle attached to a Schlenk line. Anhydrous, argon-sparged toluene (3 mL) was added and then reaction was stirred at 100 ˚C for 12 hours. The reaction mixture was diluted with 5 mL of EtOAc and the organic phase washed with water (5 mL x 3) and then with brine (5 mL) directly in the vial, removing aqueous layers after each wash using a pipette. The organic layer was dried over anhydrous sodium sulfate, filtered through a cotton plug, and then concentrated via rotary evaporation. The crude mixture was purified via silica gel column chromatography (0 to 100% hexanes / EtOAc) to yield the title compound as a white solid (26 mg, 0.100 mmol, 90% yield).1H NMR (600 MHz, CDCl3) δ 7.40 – 7.36 (m, 2H), 7.35 – 7.27 (m, 5H), 7.19 – 7.14 (m, 2H), 7.15 – 7.12 (m, 2H), 7.08 – 7.05 (m, 1H), 6.95 (td, J = 7.4, 1.3 Hz, 1H), 2.41 (s, 3H).13C NMR (151 MHz, CDCl3) δ 143.53, 143.14, 142.83, 141.27, 138.44, 129.81, 128.76, 128.26, 128.08, 124.39, 121.32, 120.26, 118.12, 116.78, 21.69. HRMS (ESI+) Calculated for C19H18N (M+H)+: 260.1439, found: 260.1439. Preparation of (4-((((6-(p-tolyl)naphthalen-2-yl)carbamoyl)oxy)methyl)phenyl)boro-nic acid TIDA ester (22) FH12768200.3 UIX-05025 In an argon filled glovebox, an oven dried 40 mL vial equipped with a stir bar was charged with 21 (50 mg, 0.088 mmol, 1 equiv) 20 (29 mg, 0.13 mmol, 1.5 equiv.), TMSOK (17 mg, 0.13 mmol, 1.5 equiv) and Pd-P(tBu)3-G4 precatalyst (5 mg, 0.009 mmol, 0.1 equiv). The vial was sealed with a PTFE septum cap, removed from the glovebox, and placed under positive argon pressure via a needle attached to a Schlenk line. Anhydrous, argon-sparged THF (4 mL) was added and the reaction was stirred at 50 ˚C for 1.5 hour. The reaction mixture was diluted with hexane (30 mL) and filtered through a silica plug. The silica plug was washed with Et2O (40 mL) and the ether eluent was discarded. The silica plug was washed with EtOAc (40 mL) and then the solution was concentrated via rotary evaporation to yield 22 (48 mg, 94% yield).1H NMR (600 MHz, CDCl3) δ 8.02 (s, 1H), 7.95 (s, 1H), 7.83 (d, J = 8.5 Hz, 2H), 7.72 (d, J=8.5Hz, 1H), 7.60 (d, J=7.6Hz, 4H), 7.41-7.37 (m, 3H), 7.29 (d, J=7.77Hz, 2H), 6.84 (s, 1H), 5.26 (s,2H), 2.49 (s, 3H), 2.42 (s, 3H), 1.80 (s, 6H), 1.54 (s, 6H).13C NMR (151 MHz, CDCl3) δ 174.63, 138.10, 137.48, 137.13, 137.08, 135.12, 134.31, 132.98, 130.53, 129.59, 129.19, 127.87, 127.54, 127.10, 126.31, 125.11, 66.87, 37.38, 21.14. HRMS (ESI+) Calculated for C34H35BN2O6 (M+H)+: 578.4720, found: 578.2552. Preparation of 6-(p-tolyl)naphthalen-2-amine (23) Following general deprotection procedure A, using 22 ( 48 mg, 0.083 mmol, 1 equiv), NaBH4(94 mg, 30.0 equiv, 2.48 mmol), 10% Pd / C (10 wt%, 5mg) afforded 23, a white solid (17.50 mg, 90%). FH12768200.3 UIX-050251H NMR (600 MHz, CDCl3) δ 7.88 ( s, 1H), 7.71 (d, J=8.5Hz, 1H), 7.65 (s, 2H), 7.59 ( d, J=8.2Hz, 2H), 7,28 (d, J=88Hz, 2H), 7.00 (s, 1H), 6.97 (dd, J1= 2.3Hz, J2=8.8Hz, 1H), 3.88 (s, 2H), 2.41 (s, 3H).13C NMR (151 MHz, CDCl3) δ 144.15, 138.52, 136.58, 135.16, 134.00, 129.51, 128.21, 126.94, 126.25, 126.01, 125.35, 118.60, 108.38, 21.11. HRMS (ESI+) Calculated for (M+H)+: 234.1283, found: 234.1285. Preparation of N-(6-(p-tolyl)naphthalen-2-yl)benzamide (25) Compound 23 (7.7 mg, 0.033 mmol, 1 equiv) and benzoyl chloride (24, 5.6 mg, 0.043 mmol, 1.22 equiv) were added to an oven-dried 40 mL vial with a stir bar. The vial was sealed with a PTFE septum cap, and then evacuated and backfilled with nitrogen (3x) via a needle attached to a Schlenk line. Freshly distilled pyridine (2 mL) was added by syringe. The mixture was then placed in a pre-equilibrated 50° C heat block and stirred for 12 hours. The solvent was concentrated on a rotary evaporator using a water bath temperature of 70° C. Water (4 ml) was added, and then the solution was basified to pH 10 with 6 N NaOH, then acidified to pH=4 with 1N HCl and lastly neutralized pH=7 with 10% Sodium Bicarbonate. The aqueous solution was extracted with dichloromethane (2×10 mL), and the collected organic phase dried over anhydrous sodium sulfate. The crude reaction mixture was purified by silica gel column chromatography eluting with 0 to 25% EtOAc / hexanes to yield the title compound as a white solid (9.7mg, 0.028mmol, 88% yield).1H NMR (600 MHz,CDCl3) δ 8.38 (d, J=2.2Hz, 1H), 7.98 (d, J=7.2Hz, 2H), 7.94 (d, J=8.0Hz, 2H), 7.90 (dd, J1=2.6Hz, J2= 8.4Hz, 2H), 7.75 (dd, J1=1.8Hz, J2= 8.4Hz, 1H), 7.63-7.57 (m, 4H), 7.53 (t, J= 7.1Hz, 2H), 7.30 ( d, J=7.9Hz, 2H), 2.43 (s, 3H)13C NMR (151 MHz, CDCl3) δ 165.78, 138.10, 137.85, 137.14, 135.32, 135.0, 132.94, 131.97, 131.08, 129.62, 129.14, 128.90, 128.21, 127.15, 127.04, 126.32, 125.13, 120.37, 116.73, 21.15 HRMS (ESI+) Calculated for C24H19NO (M+H)+:338.1545, found:338.1543. FH12768200.3 UIX-05025 Preparation of (4-((((4'-(dimethylamino)-[1,1'-biphenyl]-3- yl)carbamoyl)oxy) methyl)phenyl)boronic acid, TIDA ester (27) In an argon filled glovebox, an oven dried 40 mL vial equipped with a stir bar was charged with 5 (10 mg, 0.019 mmol, 1 equiv) 26 (6.76mg, 0.03 mmol, 1.5 equiv.), TMSOK (4 mg, 0.03 mmol, 1.5 equiv) and Pd-P(tBu)3-G4 precatalyst (1.11 mg, 0.002 mmol, 0.1 equiv). The vial was sealed with a PTFE septum cap, removed from the glovebox, and placed under positive argon pressure via a needle attached to a Schlenk line. Anhydrous, argon-sparged THF (4 mL) was added and the reaction was stirred at 50 ˚C for 1.5 hour. The reaction mixture was diluted with hexane (30 mL) and filtered through a silica plug. The silica plug was washed with Et2O (40 mL) and the ether eluent was discarded. The silica plug was washed with EtOAc (40 mL) and then the solution was concentrated via rotary evaporation to yield 27 (10 mg, 92% yield).1H NMR (600 MHz,CDCl3) δ1H NMR (500 MHz, CDCl3) δ 7.6 (d, J = 8.0 Hz, 3H), 7.5 (d, J = 8.4 Hz, 2H), 7.4 (d, J = 7.7 Hz, 2H), 7.3 (d, J = 7.4 Hz, 2H), 7.3 (t, J = 2.3 Hz, 1H), 6.8 (d, J = 10.3 Hz, 3H), 5.2 (s, 2H), 3.0 (s, 6H), 2.5 (s, 3H), 1.8 (s, 6H), 1.5 (s, 6H).13C NMR (151 MHz, CDCl3) δ 174.7, 153.4, 142.1, 138.1, 137.2, 134.3, 129.4, 129.1, 127.5, 121.6, 116.5, 112.9, 71.8, 66.7, 37.4, 21.3. HRMS (ESI+) Calculated for C24H19NO (M+H)+:558.2775 , found:.558.2777. Preparation of N4',N4'-dimethyl-[1,1'-biphenyl]-3,4'-diamine (28) FH12768200.3 UIX-05025 Following general deprotection procedure A, using 27 (14.10mg, 0.025 mmol, 1 equiv), NaBH4(28.71mg, 30.0 equiv, 0.79 mmol), 10% Pd / C (10 wt%, 1.5mg) afforded free amine 28 as a red solid (5mg, 93%).1H NMR (600 MHz,CDCl3) 7.6 – 7.4 (m, 2H), 7.2 (t, J = 7.8 Hz, 1H), 7.0 (dt, J = 7.8, 1.3 Hz, 1H), 6.9 (t, J = 2.0 Hz, 1H), 6.8 (d, J = 8.4 Hz, 2H), 6.6 (dd, J = 8.0, 2.3 Hz, 1H), 3.0 (s, 6H).13C NMR δ 150.0, 146.6, 142.4, 129.5, 129.4, 127.6, 117.0, 113.1, 113.0, 112.7, 40.6. HRMS (ESI+) Calculated for C24H19NO (M+H)+: 213.1394, found: 213.1392. Preparation of N-(4'- (dimethylamino)-[1,1'-biphenyl]-3-yl)p entanamide (30) Compound 28 (31 mg, 0.146 mmol, 1 equiv) and pentanoyl chloride (29, 21.48 mg, 0.178 mmol, 1.22 equiv) were added to an oven-dried 40 mL vial with a stir bar. The vial was sealed with a PTFE septum cap, and then evacuated and backfilled with nitrogen (3x) via a needle attached to a Schlenk line. Freshly distilled pyridine (4 mL) was added by syringe. The mixture was then placed in a pre-equilibrated 50° C heat block and stirred for 12 hours. The solvent was concentrated on a rotary evaporator using a water bath temperature of 70° C. Water (4 ml) was added, and then the solution was basified to pH 10 with 6 N NaOH. The aqueous solution was extracted with dichloromethane (2×10 mL), and the collected organic phase dried over anhydrous sodium sulfate and obtained crude product (orange liquid). The orange liquid was purified by silica gel column chromatography eluting with 0 to 50% EtOAc / hexanes to yield the title compound as a white solid (15mg, 0.051mmol, 35% yield). FH12768200.3 UIX-050251H NMR (500 MHz, CDCl3) δ 7.7 (s, 1H), 7.5 (d, J = 8.4 Hz, 2H), 7.4 (d, J = 7.8 Hz, 1H), 7.3 (dt, J = 15.8, 7.8 Hz, 2H), 7.2 (s, 1H), 6.8 (d, J = 8.2 Hz, 2H), 3.0 (s, 6H), 2.4 (t, J = 7.6 Hz, 2H), 1.4 (sextet, J = 7.4 Hz, 2H), 1.0 (t, J = 7.4 Hz, 3H).13C NMR δ 170.4, 141.0, 137.3, 128.2, 126.8, 121.1, 116.6, 116.5, 111.9, 39.7, 36.6, 26.7, 21.4, 12.8. HRMS (ESI+) Calculated for C19H24N2O (M+H)+: 297.1967 , found: 297.1959. Preparation of (4-((((3-isopropyl-5-((4-methoxyphenyl)amino) phenyl) carbamoyl) oxy)methyl)phenyl)boronic acid, TIDA ester (33) In an argon filled glovebox, an oven dried 40 mL vial equipped with a stir bar was charged with 32 (100 mg, 0.178 mmol, 1 equiv), 31 (33.03 mg, 0.268 mmol, 1.5 equiv), SPhos G4(14.25 mg, 0.014 mmol, 0.1 equiv) and t-BuONa (25.78 mg, 0.268 mmol, 1.5 equiv). The vial was sealed with a PTFE septum cap, removed from the glovebox, and placed under positive pressure of argon via a needle attached to a Schlenk line. Anhydrous, argon-sparged toluene (4 mL) was added and then reaction was stirred at 100 ˚C for 12 hours. The reaction mixture was diluted with 5 mL of EtOAc and the organic phase washed with water (5 mL x 3) and then with brine (5 mL) directly in the vial, removing aqueous layers after each wash using a pipette. The organic layer was dried over anhydrous sodium sulfate, filtered through a cotton plug, and then concentrated via rotary FH12768200.3 UIX-05025 evaporation. The crude mixture was purified via silica gel column chromatography (0 to 100% hexanes / EtOAc) to yield the title compound as a white solid (91 mg, 0.151 mmol, 84% yield).1H NMR (500 MHz, CDCl3) δ: 7.5 (d, J = 7.8 Hz, 2H), 7.3 (d, J = 7.8 Hz, 2H), 7.1 (d, J = 8.8 Hz, 2H), 6.8 (d, J = 8.9 Hz, 2H), 6.7 (s, 1H), 6.7 (s, 1H), 6.5 (s,1H), 5.2 (s, 2H), 3.8 (s, 3H), 2.8 (septet, J = 6.9 Hz, 1H), 1.8 (s, 7H), 1.5 (s, 7H), 1.2 (d, J = 6.9 Hz, 6H).13C NMR (126 MHz, CDCl3) δ 174.7, 155.3, 153.2, 151.2, 145.9, 138.7, 137.3, 135.4, 134.2, 134.2, 127.4, 127.4, 122.4, 114.7, 109.0, 108.1, 103.3, 66.5, 55.6, 37.3, 34.3, 23.9, 23.8. HRMS (ESI+) Calculated for C33H40BN3O7, (M+H)+: 602.3038 , found: 602.3038. Preparation of 5-isopropyl-N1-(4-methoxyphenyl)benzene-1,3-diamine (34) Following general deprotection procedure A, using 33 (91mg, 0.151 mmol, 1 equiv), NaBH4(171.7 mg, 30.0 equiv, 4.54 mmol), 10% Pd / C (10 wt%, 1.5mg) afforded a solid (15 mg, 38%).1H NMR (600 MHz,CDCl3) δ 7.1 (d.1 (t, J = 1.8 Hz, 1H), 3.8 (s, 3H), 2.9 – 2.6 (septet, 1H), 1.2 (d, J = 6.9 Hz, 6H).13C NMR (126 MHz, CDCl3) δ 155.1, 151.5, 147.4, 146.2, 135.9, 122.4, 114.6, 105.2, 105.1, 99.8, 55.6, 34.2, 23.9. HRMS (ESI+) Calculated for C16H20N2O, (M+H)+: 257.1654, found: 257.1650. In an argon filled glovebox, an oven dried 40 mL vial equipped with a stir bar was charged with 35 (11 mg, 0.052 mmol, 1 equiv), 34 (15.8 mg, 0.062 mmol, 1.5 equiv), Pd(OAc)2(1.15 mg, FH12768200.3 UIX-05025 0.005 mmol, 0.1 equiv), Cs2CO3(23.3 mg, 0.072 mmol, 1.4 equiv) and rac-BINAP (6.37 mg, 0.01 mmol, 0.2equiv). The vial was sealed with a PTFE septum cap, removed from the glovebox, and placed under positive pressure of argon via a needle attached to a Schlenk line. Anhydrous, argon- sparged toluene (4 mL) was added and then reaction was stirred at 120 ˚C for 16 hours. The reaction mixture was diluted with 5 mL of EtOAc and the organic phase washed with 2M HCL (2mL x 2) and then with brine (3 mL) directly in the vial, removing aqueous layers after each wash using a pipette. The organic layer was dried over anhydrous sodium sulfate, filtered through a cotton plug, and then concentrated via rotary evaporation. The crude mixture was purified via silica gel column chromatography (0 to 100% hexanes / EtOAc) to yield the title compound as a white solid (8 mg, 0.02 mmol, 52% yield).1H NMR (500 MHz, CDCl3) δ 7.8 (d, J = 8.4 Hz, 2H), 7.0 (d, J = 8.8 Hz, 2H), 6.9 (d, J = 8.9 Hz, 2H), 6.8 (d, 8.8 Hz, 2H), 6.5 (s, 1H), 6.4 (s, 1H), 6.4 (s, 1H), 3.8 (s, 3H), 3.7 (s, 3H), 2.7 (septet, 1H), 1.1 (d, J = 6.9 Hz, 6H).13C NMR (126 MHz, CDCl3) δ 167.0, 155.5, 151.7, 148.2, 146.4, 141.7, 135.3, 131.4, 128.2, 122.7, 120.8, 114.7, 109.8, 108.9, 104.5, 55.6, 51.7, 34.3, 23.9. HRMS (ESI+) Calculated for C16H20N2O, (M+H)+: 391.4910, found: 391.2014. Example 4: Manual Synthesis of Imatinib A schematic of the synthesis of imatinib is shown below. FH12768200.3 UIX-05025 In an argon filled glovebox, an oven dried 40 mL vial equipped with a stir bar was charged with 38 (100 mg, 0.19 mmol, 1 equiv) 37 (61 mg, 0.38 mmol, 2 equiv.), TMSOK (42 mg, 0.33 mmol, 1.7 equiv) and Pd-RuPhos-G4 precatalyst (16 mg, 0.019 mmol, 0.1 equiv). The vial was sealed with a PTFE septum cap, removed from the glovebox and B(OTMS)3(0.2 mL, 0.57 mmol, 3 equiv) followed by anhydrous THF (4 mL) were added via syringe. The vial was placed in a pre- equilibrated aluminum heating block set to 78 ˚C and stirred at 500 rpm overnight. The vial was removed from the heating block and allowed to cool to room temperature. The reaction mixture was diluted with hexane (30 mL) and filtered through a silica plug. The plug was washed with hexanes (100 mL), Et2O (100 mL) and EtOAc (100 mL), and then the eluents were discarded. The silica plug was then washed with acetone (200 mL) to elute the product. The acetone eluent was concentrated via rotary evaporation to yield 39 as a white solid (54.2 mg, 54% yield).1H NMR (600 MHz, CDCl3) δ 9.29 (d, J = 2.4 Hz, 1H), 8.83 (s, 1H), 8.73 – 8.68 (m, 1H), 8.63 (dd, J = 5.5, 2.0 Hz, 1H), 8.39 (dd, J = 8.0, 2.3 Hz, 1H), 7.56 (dd, J = 7.9, 2.1 Hz, 2H), 7.43 – 7.38 (m, 4H), 5.27 (d, J = 2.0 Hz, 2H), 2.48 (d, J = 2.1 Hz, 3H), 1.85-1.70 (m, 6H), 1.59-1.45 (m, 6H).13C NMR (151 MHz, CDCl3) δ 174.78, 163.25, 159.48, 157.99, 152.01, 151.72, 148.58, 136.87, 134.98, 132.02, 127.91, 123.97, 111.76, 67.28, 37.50.11B NMR (161 MHz, CDCl3) δ 8.73. HRMS (ESI+) Calculated for C26H29BN5O6(M+H)+: 518.2211, found: 518.2232. Manual deprotection of 39 to prepare 4-(pyridin-3-yl)pyrimidin-2-amine (40) FH12768200.3 UIX-05025 To a 40 mL vial with a stir bar was added 39 (50 mg, 0.096 mmol, 1.0 equiv), NaBH4(0.1 g, 2.90 mmol, 30.0 equiv,) and 10 wt % of 10% Pd / C (5 mg). Using a needle attached to a Schlenk line, the vial was evacuated and backfilled with nitrogen (3x) and then MeOH (3 mL) was added by syringe. An empty (deflated) balloon attached to a needle was placed through the septum to avoid loss of generated hydrogen without buildup of excess pressure and then the reaction was stirred at 68 ˚C for 2 hours. The reaction mixture was diluted with hexanes (30 mL) and filtered throug a silica plug. The plug was washed with hexanes (100 mL), Et2O (100 mL) and EtOAc (100 mL) and then the eluent was discarded. The the silica plug was washed with acetone (250 mL) to release the product. The acetone eluent was then concentrated via rotary evaporation to yield 40 as a white solid (12.2 mg, 75% yield).1H NMR (400 MHz, CDCl3) δ 9.20 (d, J = 2.1 Hz, 1H), 8.70 (d, J = 4.9 Hz, 1H), 8.39 (d, J = 5.2 Hz, 1H), 8.34 – 8.27 (m, 1H), 7.41 (dd, J = 8.1, 4.8 Hz, 1H), 7.07 (d, J = 5.2 Hz, 1H). The data are in agreement with data from the literature: J. Kang, J.Y. Lee, J-H. Park, D-J. Chang, J. Label Compd. Radiopharm., 2020, 63:174–182. In an argon filled glovebox, an oven dried 40 mL vial equipped with a stir bar was charged with 40 (20 mg, 0.11 mmol, 1.0 equiv), 41 (185 mg, 0.35 mmol, 3.0 equiv), Cs2CO3(75 mg, 0.232 mmol, 2.0 equiv), and XantPhos-Pd-G3 (22 mg, 0.023 mmol, 0.2 equiv). The vial was sealed with a PTFE septum cap, removed from the glovebox, and placed under positive pressure of argon via FH12768200.3 UIX-05025 needle attached to a Schlenk line. Anhydrous dioxane (3 mL) was added via syringe. The vial was placed in a pre-equilibrated aluminum heating block set to 100 ˚C and stirred at 600 rpm for 12 hours. The vial was removed from the heating block and allowed to cool to room temperature. The reaction mixture was diluted with hexane (30 mL) and filtered through a silica plug. The silica plug was washed with hexanes (100 mL), Et2O (100 mL) and EtOAc (100 mL) then the eluents were discarded. The silica plug was washed with acetone (250 mL) to elute 42. The acetone eluent was concentrated via rotary evaporation to 42 as a white solid (44 mg, 60% yield).1H NMR (600 MHz, CDCl3) δ 9.25 (d, J = 2.2 Hz, 1H), 8.71 (dd, J = 5.0, 1.6 Hz, 1H), 8.50 (d, J = 5.1 Hz, 1H), 8.49 – 8.45 (m, 1H), 8.35 (s, 1H), 7.57 (d, J = 7.6 Hz, 2H), 7.43 – 7.35 (m, 3H), 7.18 (d, J = 5.1 Hz, 1H), 7.15 (d, J = 8.2 Hz, 1H), 7.05 (d, J = 8.3 Hz, 1H), 6.99 (s, 1H), 6.75 (s, 1H), 5.21 (s, 2H), 2.48 (s, 3H), 2.32 (s, 3H), 1.85-1.72 (m, 6H), 1.59-1.45 (m, 6H).13C NMR (151 MHz, CDCl3) δ 174.78, 162.89, 160.65, 159.19, 151.60, 148.65, 137.98, 137.43, 135.08, 134.38, 130.96, 127.61, 123.88, 108.59, 66.78, 37.51, 17.69.11B NMR (161 MHz, CDCl3) δ 9.04. HRMS (ESI+) Calculated for C33H36BN6O6(M+H)+: 623.2789, found: 623.2797. To a 40 mL vial with a stir bar was added 42 (44 mg, 0.064 mmol, 1 equiv) and then THF (5 mL) was added by syringe. The solution was vigorously stirred and then 3 M aqueous LiOH*(300 μL, 1.3 mmol, 15 equiv) was added by syringe. Aqueous 30% H2O2(200 μL) was added by syringe, the vial was sealed tightly with a PTFE septum cap, the vial was placed in a pre- equilibrated 55oC heating block, and then the reaction was stirred for 12 hours. The reaction mixture was diluted with hexane (30 mL) and filtered through a silica plug. Then silica plug was washed with hexanes (100 mL), Et2O (100 mL) and EtOAc (100 mL) and then the eluents were FH12768200.3 UIX-05025 discarded. The silica plug was washed with acetone (250 mL) to elute the product. The acetone eluent was concentrated via rotary evaporation and to 43 as a white solid (11 mg, 60% yield).*NaOH can be used as an alternative base. LiOH provides a milder option for deprotection.1H NMR (500 MHz, CDCl3) δ 9.26 (s, 1H), 8.71 (d, J = 4.0 Hz, 1H), 8.50 (d, J = 5.2 Hz, 1H), 8.35 (d, J = 8.1 Hz, 1H), 7.61 (s, 1H), 7.43 (dd, J = 8.0, 4.8 Hz, 1H), 7.15 (d, J = 5.2 Hz, 1H), 7.00 (d, J = 8.0 Hz, 2H), 6.42 (dd, J = 8.0, 2.4 Hz, 1H), 2.25 (s, 3H). Preparation of N-(4-methyl-3-((4-(pyridin-3-yl)pyrimidin-2-yl)amino)phenyl)-4-((4- methylpiperazin-1-yl)methyl)benzamide (Imatinib) 43 (10 mg, 0.036 mmol, 1 equiv) and 4-(4-methyl-piperazinomethyl)-benzoyl chloride (44, 11 mg, 0.043 mmol, 1.22 equiv) were added to an oven-dried 40 mL vial with a stir bar. The vial was sealed with a PTFE septum cap, and then evacuated and backfilled with nitrogen (3x) via a needle attached to a Schlenk line. Freshly distilled pyridine (2 mL) was added by syringe. The mixture was then placed in a pre-equilibrated 50° C heat block and stirred for 12 hours. The solvent was concentrated on a rotary evaporator using a water bath temperature of 70° C. Water (4 ml) was added, and then the solution was basified to pH 10 with 6 N NaOH. The aqueous solution was extracted with dichloromethane (2×10 mL), and the collected organic phase dried over anhydrous sodium sulfate. The crude reaction mixture was resuspended in 1:1 H2O:ACN 0.1% Formic Acid for preparative HPLC purification with an Agilent 10 Prep-C18250 x 50.0mm column. The final product imatinib was isolated as a white solid (12 mg, 68% yield). MHz, DMSO) δ 10.18 (s, 1H), 9.28 (s, 1H), 8.99 (s, 1H), 8.68 (dd, J = 4.8, 1.7 Hz, 1H), 8.51 (d, J = 5.1 Hz, 1H), 8.48 (dt, J = 8.0, 1.9 Hz, 1H), 8.11 (d, J = 2.2 Hz, 1H), 7.91 (d, J = 8.0 Hz, 2H), 7.53 – 7.47 (m, 2H), 7.45 – 7.40 (m, 3H), 7.20 (d, J = 8.3 Hz, 1H), 3.51 (s, 2H), 2.50- 2.23 (m, 8H), 2.24 (s, 3H) 2.13 (s, 3H). Consistent with literature spectral data.13C NMR (151 MHz, DMSO) δ 165.27, 161.61, 161.20, 159.46, 151.38, 148.22, 142.11, 137.81, 137.24, 134.42, 133.78, 132.23, 130.04, 128.62, 127.60, 123.77, 117.20, 116.74, 107.51, 61.64, 54.70, 52.58, 45.74, 17.69. FH12768200.3 UIX-05025 HRMS (ESI+) Calculated for C29H32N7O (M+H)+: 494.2668, found: 494.2671. Example 5: Automated Synthesis of Trimers via Iterative N-C and C-C Bond Formation Following the general automated procedures as described in Example 7 on 0.25 mmol scale of 21 (141.81 mg, 0.25 mmol, 1 equiv) and using the same reaction stoichiometries as described for the manual synthesis, 25 was isolated as a white solid (28 mg, 0.083 mmol, 33% overall yield). Yields and purities of intermediates were not checked. Characterization data for 23 match those reported in the manual synthesis section. FH12768200.3 UIX-05025 Following the general automated procedures as described in Example 7 on 0.33 mmol scale of 5 (170 mg, 0.33 mmol, 1 equiv) and using the same reaction stoichiometries as described for the manual synthesis, 30 was isolated as a white solid (17 mg, 0.057 mmol, 17% overall yield). Yields and purities of intermediates were not checked. Characterization data for 30 match those reported in the manual synthesis section. Automated synthesis of methyl 4-((3-isopropyl-5-((4- Following the general automated procedures as described in Example 7 on 0.358 mmol scale of 30 (200 mg, 0.358 mmol, 1 equiv) and using the same reaction stoichiometries as described for the manual synthesis, 34 was isolated as a white solid (12 mg, 0.031 mmol, 11% overall yield). Yields and purities of intermediates were not checked. Characterization data for 34 match those reported in the manual synthesis section. FH12768200.3 UIX-05025 Example 6: Automated Synthesis of Imatinib Following the general automated procedures as described in Example 7 on 0.19 mmol scale of 38 (100 mg, 0.19 mmol, 1 equiv) and using the same reaction stoichiometries as described for the manual synthesis, Imatinib was isolated as a white solid (2.0 mg, 0.004 mmol, 2.1% overall yield). For the overall yield we are reporting of the fully automated sequence, yields and purities of intermediates were not checked. Characterization data for Imatinib match those reported in the manual synthesis section. Example 7: Construction and Operation of the Automated Synthesis Platform The automated synthesis machine was constructed using the same reconfigurable valves and syringe pumps as our prior reported iterative small molecule synthesizers in a unique configuration suited driven by custom LabVIEW software. Each reaction vial was connected to the solvent reservoirs via 18-gauge syringe needle, PEEK tubing, and Luer lock fittings, through four computer-controlled 9-port 4-valve modules and two computer-controlled syringe pumps (10 mL main pump and 10 mL wet pump). The synthesis machine uses many of the engineering controls optimized for reaction reproducibility from our now published studies of closed-loop optimization of general reaction conditions, notably symmetrically circular aluminium heating blocks, an automated Schlenk line driven by J-Kem valve modules, magnetic heating plates, rare earth stir bars, and Leur-lock cap solvent inert manifold, as well as our rapid automated iterative small molecule synthesizer, notably an automated rotary evaporator (see further improvements FH12768200.3 UIX-05025 below). The LabVIEW code was modified to account for the unique fluid path of this prototype configuration. The solvents attached to the dry pump were stored in 250 mL to 1L Pyrex glass media bottles and connected via PEEK tubing, Luer lock fittings, and 3-port Cole-Parmer VapLock solvent delivery caps to both the argon manifold and the valve modules. One of the three ports on each solvent cap was connected to the argon manifold and one to PEEK tubing reaching the bottom of the solvent bottles (dip tube). The last port was capped. The full argon manifold was connected to a plugged passive 9-port valve (vent port). Solvents refilled on the system were degassed by argon purging for one hour. Degassing was accomplished by first depressurizing the manifold by uncapping the third port on the solvent cap and dipping the line connected to the argon manifold into the solvent (sparging begins). Following the degassing time, argon sparging is ceased by pulling the argon line out of the solvent and capping the open port. In this way, solvents could be refilled and degassed individually while pressure differences between solvents on the manifold cannot result in redistribution or mixing. Solvents attached to the wet pumps were added to 40 mL I-Chem vials and used immediately before any aqueous reaction. Automated rotary evaporation was accomplished as described in our prior report. The automated Schlenk Process utilizes a Fisherbrand™ Maxima Rotary Vane Vacuum Pumps – 115 V, 60 Hz and autoSchlenk processes operated via alternating between 60 seconds of vacuum and 5 seconds of argon pressure cycles (valve module). The argon cylinder was maintained at ~4 PSI regulator setting throughout the study to ensure appropriate pressure at each position. A standard 10 cycles of autoschlenk (<15 min) was used to deoxygenize the system prior to executing automated synthesis procedures. AutoSchlenk is also useful for drying residual solvent vapours from the manifold in between automated runs or after automated cleaning procedures. Vacuum draining during the automated purification used a KNF Neuberger Vacuum Diaphragm Pump connected to the headspace of a 3-port Cole-Parmer VapLock solvent delivery cap on a 1L Pyrex glass media bottle (the vacuum drained solvent is collected at the bottom of this bottle and is discarded between runs), and the pump is vented to laboratory exhaust in the same manner as the automated rotary evaporator. Buchi R-100 rotovap with Buchi V-100 vacuum pump and I-100 interface. FH12768200.3 UIX-05025 Modules description Design of Anhydrous Suzuki Coupling Module The anhydrous Suzuki coupling module consists of one 40 mL 9-Chem vial. The coupling module contains catalyst, halide, TMSOK, and neopentyl ester, and a 10 mm diameter rare earth Teflon coated stir bar. The main pump transfers reaction solvent into the coupling module. The coupling module is then stirred at the desired rpm until reaction completion. The reaction is then purified via catch-and-release. The release solvent is transferred to the anhydrous deprotection module and concentrated prior to deprotection. Design of Anhydrous Deprotection Module The anhydrous deprotection module consists of one 40 mL I-Chem vial. Upon concentration of solvent, the deprotection cartridge is loaded with NaBH4and Pd on Carbon (10% wt), and 10mm diameter rare earth Teflon coated stir bar. During addition of MeOH, a balloon is attached to prevent over pressurization while maintaining high H2atmosphere in the reaction vial. The main pump transfers solutions of TIDA boronates into the deprotection module. The deprotection cartridge is then stirred at the desired time, temperature, and rpm until reaction completion. The reaction is then purified via anhydrous catch-and-release. The release solvent is transferred through a polyethylene-fritted 12-gram Luknova cartridge containing approximately one cubic cm of celite. The celite in the filter cartridge is well packed onto the frit via wetting with hexanes followed by air drying. Design of Buchwald-Hartwig Coupling Module The Buchwald-Hartwig coupling module consists of two 40 mL I-Chem vials. The first vial is an isolation vial, where following anhydrous deprotection and filtration through a celite packed 12-gram Luknova column, the released solvent is concentrated off to dryness. Following concentration, the main pump adds reaction solvent to dissolve the deprotected amine and transfers it to the second 40 mL I-Chem vial containing halide, Cs2CO3, and catalyst. The reaction module is then stirred at the desired time, temperature, and rpm until reaction completion. The reaction is then purified via anhydrous catch-and-release. The release solvent is transferred back into the reaction vial and concentrated to a desired volume and transferred to the aqueous deprotection module via the main pump. FH12768200.3 UIX-05025 Design of Aqueous Deprotection Module The deprotection module consists of one polyethylene-fritted 12-gram Luknova cartridge and 140 mL I-Chem vial containing 3 M solution of LiOH. One filter cartridge is situated on top of the deprotection cartridge and contains approximately one cubic cm of celite. The celite in the filter cartridges is well packed onto the frit via wetting with hexanes followed by air drying. The dry pump transfers solutions of TIDA boronates through the filter cartridge and into the deprotection cartridge. The wet pump adds an aqueous solution of H2O2. The deprotection cartridge is then stirred at the desired rpm until reaction completion. The reaction is then filtered through a 12-gram Luknova cartridge containing Na2SO4into the amide coupling module. Design of Amide Coupling Module The amide coupling module consists of one 40-mL Ichem vial. Upon transferring from the aqueous deprotection module, the release solvent is concentrated to dryness. Prior to coupling, 2 40 mL I-Chem vials connected to the wet pump are filled with pyridine and a pyridine solution of carboxylic acid. The wet pump is prerinsed with pyridine by withdrawing 10 mL of pyridine and discarding it. The wet pump then withdraws the pyridine / carboxylic acid solution and adds it to the vial containing the purified deprotected amine. The deprotection cartridge is then stirred at the desired rpm until reaction completion. Design of Anhydrous Reaction Module The design of the anhydrous reaction module is shown in FIG. 7. The coupling module consists of up to 440 mL I-Chem vials (reaction cartridges) each with septa cap and equipped with rare earth Teflon coated stir bar (10 mm diameter). Each reaction cartridge is connected to the argon manifold and the valve modules via 16- and 18-gauge needles, respectively. The reaction cartridges are all simultaneously deoxygenated via an automated Schlenk process as described previously. Sensitive reagents are loaded prior to reaction. Otherwise, the reaction cartridges are preloaded with required chemicals. For reactions requiring higher temperatures, the heating block is set to the desired reaction temperature at the start of the automated reaction time. The 16-gauge needle connecting each reaction cartridge to the valve modules is connected internally to 0.125” PEEK tubing fitted on the bottom with a 20 µm end line filter (Biolytic Lab Performance Inc). FH12768200.3 UIX-05025 This dip tube enables transfer from the bottom of the reaction cartridge to any other component of the module. The reaction cartridge is also connected to the automated rotary evaporator to allow for concentration of purified reaction mixtures. Design of Aqueous Reaction Module The design of the aqueous reaction module is shown in FIG. 8. The coupling module consists of two 40 mL I-Chem vials (reaction cartridges) each with septa cap and equipped with rare earth Teflon coated stir bar (10 mm diameter). Sensitive reagents are loaded prior to reaction. Otherwise, the reaction cartridges are preloaded with required chemicals, or chemicals are transferred from elsewhere on the module. For reactions requiring higher temperatures, the heating block is set to the desired reaction temperature at the start of the automated reaction time. The 16- gauge needle connecting each reaction cartridge to the valve modules is connected internally to 0.125” PEEK tubing fitted on the bottom with a 20 µm end line filter (Biolytic Lab Performance Inc). This dip tube enables transfer from the bottom of the reaction cartridge to any other component of the module. The reaction cartridge is also connected to the automated rotary evaporator to allow for concentration of purified reaction mixtures. Design of Purification Modules The design of the purification module is shown in FIG.9. The purification module consists of one 10 gram Biotage column. The purification cartridge is made by first adding a packed bed of silica (0.75 in.) to the bottom frit. Glass beads (4 mm) are then loaded on top of the silica bed, and a 1:1 silica:sand is added to fill the dead volume. The top frit, cap, and insert are then fitted together to complete the purification cartridge. The filtration cartridge is fitted directly into the purification cartridge inline on the valve module and standing upside down. During purification, the pump adds hexane / Et2O / EtOAc directly to the reaction cartridge. This reaction solution is then vacuum filtered through the endline filter and through the filtration cartridge followed by the purification cartridge. Then, the dry / wet pump reverse elutes the two cartridges with acetone / THF into the reaction cartridge and the reaction cartridge is concentrated via automated rotary evaporation. FH12768200.3 UIX-05025 Automated Synthesis Procedures Automated Suzuki-Miyaura Coupling Procedure To a 40 mL I-Chem vial was loaded TIDA bifunctional, neopentyl ester and catalyst. The vial was placed in the coupling module aluminum heating block. An automated Schlenk-line procedure[2]was performed followed by addition of 4 mL desired solvent via dry pump. The reaction was heated and stirred for the given reaction time. Automated Anhydrous Purification Procedure To the crude reaction mixture was added hexane or ether (20 mL) via the dry pump to precipitate the TIDA boronate. The hexane / ether was then purged through the filter and purification cartridge via a diaphragm vacuum pump (20 minutes). Ether (if precipitation solvent was hexane) or Ethyl acetate (if precipitation solvent was ether) (20 mL) solution was then added to the reaction vial and purged through the filter and purification cartridge (20 minutes). This process was repeated twice. Acetone / THF was then reverse eluted (2x10 mL) and concentrated via automated rotary evaporation either to completion or a desired volume (~30 min). Automated Anhydrous Deprotection Procedure Immediately following purification of the Suzuki coupling, the THF is evacuated to dryness. The TIDA boronate is redissolved in MeOH. To the reaction cartridge containing 1 equiv. TIDA boronate is added 10 wt% Pd / C and 30 equiv NaBH4. The reaction is stirred at the desired temperature for 7 hours. Automated Buchwald-Hartwig Coupling Procedure To a 40 mL I-Chem vial was loaded TIDA bifunctional, amine, base, and catalyst. The vial was placed in the coupling module aluminum heating block. An automated Schlenk-line procedure was performed followed by addition of 4 mL desired solvent via dry pump. The reaction was heated and stirred for the given reaction time. Automated Aqueous Deprotection Procedure FH12768200.3 UIX-05025 Following the Automated Anhydrous Purification Procedure, the THF solution of purified TIDA is then transferred to a vial containing LiOH. The wet pump then adds an aqueous solution of H2O2to the vial. The reaction is then stirred at the desired time and temperature. Automated Aqueous Purification Procedure Following the Automated Aqueous Deprotection Procedure, the THF:H2O:H2O2solution is filtered through a cartridge containing Na2SO4. The deprotected product is used without any further purification. Automated Amide Coupling Procedure Following the Automated Aqueous Deprotection Procedure, the dried THF solution of amine is concentrated to dryness. A solution of carboxylic acid dissolved in 4 mL pyridine is added to dissolve the concentrated amine. The reaction is then heated to the desired temperature and stirred for the desired time. Example 8: Single-Crystal X-Ray Diffraction Data Crystal data and structure refinement for chloroformate 1 (10632ds), CCDC Number: 2291420 are provided below. Table 1. Crystal data and structure refinement for 10632ds. FH12768200.3 UIX-05025 Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters(Å2x 103) for 10632ds.U(eq) is defined as one third of the trace of the orthogonalized Uijtensor.x y z U(eq) O(1) 7075(1) 4838(1) 2890(1) 21(1) O(2) 7498(1) 6752(2) 1906(1) 30(1) O(3) 4593(1) 4981(1) 4008(1) 25(1) O(4) 5941(1) 4066(1) 3863(1) 20(1) FH12768200.3 UIX-05025 N(1) 6683(1) 6826(1) 4000(1) 17(1) C(1) 7292(1) 6413(2) 2637(1) 22(1) C(2) 7309(1) 7678(2) 3413(1) 21(1) C(3) 5699(1) 7035(2) 3697(1) 20(1) C(4) 5342(1) 5269(2) 3905(1) 19(1) C(5) 8248(1) 7617(2) 3868(1) 26(1) C(6) 7113(1) 9541(2) 3152(1) 29(1) C(7) 5260(1) 8482(2) 4163(1) 29(1) C(8) 5455(1) 7149(2) 2674(1) 27(1) C(9) 6872(1) 7300(2) 4967(1) 21(1) C(10) 7485(1) 3679(2) 4482(1) 19(1) C(11) 7229(1) 3142(2) 5305(1) 21(1) C(12) 7763(1) 2138(2) 5892(1) 23(1) C(13) 8575(1) 1625(2) 5668(1) 22(1) C(14) 8839(1) 2124(2) 4850(1) 25(1) C(15) 8302(1) 3131(2) 4266(1) 23(1) C(16) 9157(1) 559(2) 6305(1) 26(1) B(1) 6826(1) 4756(2) 3816(1) 18(1) Cl(1) 9258(1) -4390(1) 6103(1) 33(1) O(5) 9093(2) -1182(2) 5963(1) 19(1) O(6) 9750(1) -2104(2) 7288(1) 36(1) C(17) 9410(1) -2351(2) 6563(1) 21(1) Cl(2) 9137(6) -1738(10) 6163(6) 39(2) O(7) 9627(17) 1130(30) 7154(13) 36(1) Table 3. Bond lengths [Å] and angles [°] for 10632ds. O(1)-C(1) 1.3404(17) O(1)-B(1) 1.4856(16) O(2)-C(1) 1.2056(17) O(3)-C(4) 1.2055(17) O(4)-C(4) 1.3252(16) FH12768200.3 UIX-05025 O(4)-B(1) 1.4793(17) N(1)-C(9) 1.5029(16) N(1)-C(2) 1.5280(16) N(1)-C(3) 1.5522(17) N(1)-B(1) 1.6589(18) C(1)-C(2) 1.5296(19) C(2)-C(6) 1.5293(19) C(2)-C(5) 1.544(2) C(3)-C(7) 1.5258(19) C(3)-C(4) 1.5296(19) C(3)-C(8) 1.5531(19) C(5)-H(5A) 0.9800 C(5)-H(5B) 0.9800 C(5)-H(5C) 0.9800 C(6)-H(6A) 0.9800 C(6)-H(6B) 0.9800 C(6)-H(6C) 0.9800 C(7)-H(7A) 0.9800 C(7)-H(7B) 0.9800 C(7)-H(7C) 0.9800 C(8)-H(8A) 0.9800 C(8)-H(8B) 0.9800 C(8)-H(8C) 0.9800 C(9)-H(9A) 0.9800 C(9)-H(9B) 0.9800 C(9)-H(9C) 0.9800 C(10)-C(15) 1.4027(18) C(10)-C(11) 1.4044(18) C(10)-B(1) 1.5958(19) C(11)-C(12) 1.3904(19) C(11)-H(11) 0.9500 FH12768200.3 UIX-05025 C(12)-C(13) 1.393(2) C(12)-H(12) 0.9500 C(13)-C(14) 1.392(2) C(13)-C(16) 1.5002(19) C(14)-C(15) 1.392(2) C(14)-H(14) 0.9500 C(15)-H(15) 0.9500 C(16)-O(5) 1.454(2) C(16)-O(7) 1.476(15) C(16)-Cl(2) 1.806(8) C(16)-H(16A) 0.9900 C(16)-H(16B) 0.9900 C(16)-H(16C) 0.9900 C(16)-H(16D) 0.9900 C(16)-H(16E) 0.9900 C(16)-H(16F) 0.9900 Cl(1)-C(17) 1.7429(17) O(5)-C(17) 1.342(2) O(6)-C(17) 1.178(2) O(7)-H(7) 0.8400 C(1)-O(1)-B(1) 113.76(10) C(4)-O(4)-B(1) 113.54(10) C(9)-N(1)-C(2) 112.40(10) C(9)-N(1)-C(3) 110.41(10) C(2)-N(1)-C(3) 116.30(10) C(9)-N(1)-B(1) 112.72(10) C(2)-N(1)-B(1) 102.93(9) C(3)-N(1)-B(1) 101.36(9) O(2)-C(1)-O(1) 123.91(13) O(2)-C(1)-C(2) 124.84(13) O(1)-C(1)-C(2) 111.10(11) FH12768200.3 UIX-05025 N(1)-C(2)-C(6) 116.26(11) N(1)-C(2)-C(1) 101.48(10) C(6)-C(2)-C(1) 115.42(11) N(1)-C(2)-C(5) 110.67(11) C(6)-C(2)-C(5) 107.29(12) C(1)-C(2)-C(5) 105.18(11) C(7)-C(3)-C(4) 112.76(11) C(7)-C(3)-N(1) 114.30(11) C(4)-C(3)-N(1) 102.02(10) C(7)-C(3)-C(8) 109.82(12) C(4)-C(3)-C(8) 101.42(11) N(1)-C(3)-C(8) 115.58(11) O(3)-C(4)-O(4) 124.04(13) O(3)-C(4)-C(3) 124.48(13) O(4)-C(4)-C(3) 111.13(11) C(2)-C(5)-H(5A) 109.5 C(2)-C(5)-H(5B) 109.5 H(5A)-C(5)-H(5B) 109.5 C(2)-C(5)-H(5C) 109.5 H(5A)-C(5)-H(5C) 109.5 H(5B)-C(5)-H(5C) 109.5 C(2)-C(6)-H(6A) 109.5 C(2)-C(6)-H(6B) 109.5 H(6A)-C(6)-H(6B) 109.5 C(2)-C(6)-H(6C) 109.5 H(6A)-C(6)-H(6C) 109.5 H(6B)-C(6)-H(6C) 109.5 C(3)-C(7)-H(7A) 109.5 C(3)-C(7)-H(7B) 109.5 H(7A)-C(7)-H(7B) 109.5 C(3)-C(7)-H(7C) 109.5 FH12768200.3 UIX-05025 H(7A)-C(7)-H(7C) 109.5 H(7B)-C(7)-H(7C) 109.5 C(3)-C(8)-H(8A) 109.5 C(3)-C(8)-H(8B) 109.5 H(8A)-C(8)-H(8B) 109.5 C(3)-C(8)-H(8C) 109.5 H(8A)-C(8)-H(8C) 109.5 H(8B)-C(8)-H(8C) 109.5 N(1)-C(9)-H(9A) 109.5 N(1)-C(9)-H(9B) 109.5 H(9A)-C(9)-H(9B) 109.5 N(1)-C(9)-H(9C) 109.5 H(9A)-C(9)-H(9C) 109.5 H(9B)-C(9)-H(9C) 109.5 C(15)-C(10)-C(11) 117.07(12) C(15)-C(10)-B(1) 123.26(12) C(11)-C(10)-B(1) 119.54(11) C(12)-C(11)-C(10) 121.88(12) C(12)-C(11)-H(11) 119.1 C(10)-C(11)-H(11) 119.1 C(11)-C(12)-C(13) 120.02(13) C(11)-C(12)-H(12) 120.0 C(13)-C(12)-H(12) 120.0 C(14)-C(13)-C(12) 119.12(13) C(14)-C(13)-C(16) 120.74(13) C(12)-C(13)-C(16) 120.14(13) C(15)-C(14)-C(13) 120.59(13) C(15)-C(14)-H(14) 119.7 C(13)-C(14)-H(14) 119.7 C(14)-C(15)-C(10) 121.31(13) C(14)-C(15)-H(15) 119.3 FH12768200.3 UIX-05025 C(10)-C(15)-H(15) 119.3 O(5)-C(16)-C(13) 106.07(13) O(7)-C(16)-C(13) 126.7(10) C(13)-C(16)-Cl(2) 118.2(3) O(5)-C(16)-H(16A) 110.5 C(13)-C(16)-H(16A) 110.5 O(5)-C(16)-H(16B) 110.5 C(13)-C(16)-H(16B) 110.5 H(16A)-C(16)-H(16B) 108.7 C(13)-C(16)-H(16C) 107.8 Cl(2)-C(16)-H(16C) 107.8 C(13)-C(16)-H(16D) 107.8 Cl(2)-C(16)-H(16D) 107.8 H(16C)-C(16)-H(16D) 107.1 O(7)-C(16)-H(16E) 105.6 C(13)-C(16)-H(16E) 105.6 O(7)-C(16)-H(16F) 105.6 C(13)-C(16)-H(16F) 105.6 H(16E)-C(16)-H(16F) 106.1 O(4)-B(1)-O(1) 112.89(11) O(4)-B(1)-C(10) 108.30(11) O(1)-B(1)-C(10) 113.83(11) O(4)-B(1)-N(1) 101.91(10) O(1)-B(1)-N(1) 99.61(10) C(10)-B(1)-N(1) 119.70(11) C(17)-O(5)-C(16) 112.93(17) O(6)-C(17)-O(5) 127.70(19) O(6)-C(17)-Cl(1) 123.18(16) O(5)-C(17)-Cl(1) 109.12(15) C(16)-O(7)-H(7) 109.5 _____________________________________________________________ FH12768200.3 UIX-05025 Symmetry transformations used to generate equivalent atoms:Table 4. Anisotropic displacement parameters (Å2x 103) for 10632ds.The anisotropic displacement factor exponent takes the form: -2p2[ h2a*2U11+ … + 2 h k a* b*U12]______________________________________________________________________________ U11U22U33U23U13U12______________________________________________________________________________ O(1) 28(1) 20(1) 15(1) -3(1) 4(1) 0(1) O(2) 38(1) 34(1) 17(1) 1(1) 7(1) -1(1) O(3) 21(1) 33(1) 22(1) -2(1) 3(1) -2(1) O(4) 20(1) 19(1) 20(1) -1(1) 1(1) -1(1) N(1) 21(1) 17(1) 13(1) -2(1) 2(1) -1(1) C(1) 24(1) 24(1) 17(1) 0(1) 2(1) 0(1) C(2) 26(1) 19(1) 16(1) 0(1) 4(1) -4(1) C(3) 21(1) 21(1) 18(1) 0(1) 1(1) 2(1) C(4) 21(1) 23(1) 13(1) -3(1) 0(1) 0(1) C(5) 26(1) 30(1) 23(1) 1(1) 3(1) -8(1) C(6) 40(1) 20(1) 27(1) 2(1) 4(1) -4(1) C(7) 31(1) 24(1) 33(1) -3(1) 6(1) 7(1) C(8) 27(1) 31(1) 21(1) 5(1) -4(1) 1(1) C(9) 29(1) 21(1) 14(1) -4(1) 2(1) -2(1) C(10) 20(1) 16(1) 20(1) -1(1) 3(1) -1(1) C(11) 21(1) 21(1) 23(1) 2(1) 6(1) 1(1) C(12) 26(1) 21(1) 22(1) 3(1) 4(1) 0(1) C(13) 24(1) 18(1) 25(1) -1(1) -2(1) 0(1) C(14) 20(1) 25(1) 29(1) -2(1) 5(1) 3(1) C(15) 24(1) 24(1) 21(1) 0(1) 6(1) 0(1) C(16) 28(1) 21(1) 28(1) -2(1) -5(1) 1(1) B(1) 22(1) 16(1) 15(1) -2(1) 3(1) -1(1) Cl(1) 40(1) 17(1) 40(1) 2(1) -10(1) 1(1) FH12768200.3 UIX-05025 O(5) 22(1) 15(1) 19(1) 6(1) -2(1) 4(1) O(6) 50(1) 27(1) 28(1) 4(1) -17(1) 3(1) C(17) 22(1) 17(1) 22(1) 5(1) -2(1) 1(1) Cl(2) 37(3) 43(4) 39(4) -13(3) 7(3) -1(3) O(7) 50(1) 27(1) 28(1) 4(1) -17(1) 3(1)Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103)for 10632d__ y z U(e__ H(5A) 8376 6461 4099 39 H(5B) 8312 8441 4361 39 H(5C) 8654 7909 3432 39 H(6A) 7568 9976 2804 43 H(6B) 7095 10235 3692 43 H(6C) 6549 9605 2792 43 H(7A) 5539 9573 4043 44 H(7B) 5314 8272 4807 44 H(7C) 4643 8532 3938 44 H(8A) 5690 8210 2447 40 H(8B) 4821 7146 2546 40 H(8C) 5699 6164 2382 40 H(9A) 7453 6893 5189 32 H(9B) 6439 6768 5312 32 H(9C) 6846 8547 5030 32 H(11) 6674 3475 5465 26 H(12) 7573 1801 6447 28 H(14) 9391 1775 4690 30 H(15) 8493 3454 3710 27 H(16A) 9764 974 6332 31 H(16B) 8964 612 6911 31 H(16C) 9010 812 6916 31 FH12768200.3 UIX-05025 H(16D) 9762 950 6271 31 H(16E)8800 -428 6460 31 H(16F) 9607 88 5950 31 H(7) 9630 340 7532 54 Table 6. Torsion angles [°] for 10632ds. ________________________________________________________________ B(1)-O(1)-C(1)-O(2) -178.63(13) B(1)-O(1)-C(1)-C(2) 5.53(15) C(9)-N(1)-C(2)-C(6) -80.37(14) C(3)-N(1)-C(2)-C(6) 48.28(15) B(1)-N(1)-C(2)-C(6) 158.09(11) C(9)-N(1)-C(2)-C(1) 153.57(11) C(3)-N(1)-C(2)-C(1) -77.78(13) B(1)-N(1)-C(2)-C(1) 32.02(12) C(9)-N(1)-C(2)-C(5) 42.34(15) C(3)-N(1)-C(2)-C(5) 170.98(11) B(1)-N(1)-C(2)-C(5) -79.21(12) O(2)-C(1)-C(2)-N(1) 159.05(14) O(1)-C(1)-C(2)-N(1) -25.15(14) O(2)-C(1)-C(2)-C(6) 32.4(2) O(1)-C(1)-C(2)-C(6) -151.76(12) O(2)-C(1)-C(2)-C(5) -85.59(17) O(1)-C(1)-C(2)-C(5) 90.21(13) C(9)-N(1)-C(3)-C(7) 32.63(15) C(2)-N(1)-C(3)-C(7) -96.97(13) B(1)-N(1)-C(3)-C(7) 152.30(11) C(9)-N(1)-C(3)-C(4) -89.39(12) C(2)-N(1)-C(3)-C(4) 141.01(10) B(1)-N(1)-C(3)-C(4) 30.28(11) C(9)-N(1)-C(3)-C(8) 161.56(11) FH12768200.3 UIX-05025 C(2)-N(1)-C(3)-C(8) 31.96(16) B(1)-N(1)-C(3)-C(8) -78.77(13) B(1)-O(4)-C(4)-O(3) -174.69(12) B(1)-O(4)-C(4)-C(3) 11.86(14) C(7)-C(3)-C(4)-O(3) 35.45(18) N(1)-C(3)-C(4)-O(3) 158.52(12) C(8)-C(3)-C(4)-O(3) -81.92(15) C(7)-C(3)-C(4)-O(4) -151.13(11) N(1)-C(3)-C(4)-O(4) -28.07(13) C(8)-C(3)-C(4)-O(4) 91.49(12) C(15)-C(10)-C(11)-C(12) 1.2(2) B(1)-C(10)-C(11)-C(12) 177.10(13) C(10)-C(11)-C(12)-C(13) -0.5(2) C(11)-C(12)-C(13)-C(14) -0.3(2) C(11)-C(12)-C(13)-C(16) 179.26(13) C(12)-C(13)-C(14)-C(15) 0.4(2) C(16)-C(13)-C(14)-C(15) -179.18(13) C(13)-C(14)-C(15)-C(10) 0.4(2) C(11)-C(10)-C(15)-C(14) -1.1(2) B(1)-C(10)-C(15)-C(14) -176.86(13) C(14)-C(13)-C(16)-O(5) -77.58(18) C(12)-C(13)-C(16)-O(5) 102.89(17) C(14)-C(13)-C(16)-O(7) 108.1(14) C(12)-C(13)-C(16)-O(7) -71.5(14) C(14)-C(13)-C(16)-Cl(2) -85.1(3) C(12)-C(13)-C(16)-Cl(2) 95.4(3) C(4)-O(4)-B(1)-O(1) -97.26(13) C(4)-O(4)-B(1)-C(10) 135.76(11) C(4)-O(4)-B(1)-N(1) 8.66(13) C(1)-O(1)-B(1)-O(4) 122.32(12) C(1)-O(1)-B(1)-C(10) -113.68(13) FH12768200.3 UIX-05025 C(1)-O(1)-B(1)-N(1) 14.94(13) C(15)-C(10)-B(1)-O(4) 137.71(13) C(11)-C(10)-B(1)-O(4) -37.95(16) C(15)-C(10)-B(1)-O(1) 11.28(18) C(11)-C(10)-B(1)-O(1) -164.39(12) C(15)-C(10)-B(1)-N(1) -106.25(15) C(11)-C(10)-B(1)-N(1) 78.09(16) C(9)-N(1)-B(1)-O(4) 93.43(12) C(2)-N(1)-B(1)-O(4) -145.23(10) C(3)-N(1)-B(1)-O(4) -24.58(11) C(9)-N(1)-B(1)-O(1) -150.54(10) C(2)-N(1)-B(1)-O(1) -29.20(12) C(3)-N(1)-B(1)-O(1) 91.45(10) C(9)-N(1)-B(1)-C(10) -25.90(16) C(2)-N(1)-B(1)-C(10) 95.44(13) C(3)-N(1)-B(1)-C(10) -143.91(11) C(13)-C(16)-O(5)-C(17) -165.15(17) C(16)-O(5)-C(17)-O(6) -3.3(3) C(16)-O(5)-C(17)-Cl(1) 177.34(13) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms Crystal data and structure refinement for 5 (10631ds), CCDC Number: 2290142 are provided below. Table 7. Crystal data and structure refinement for 10631ds. FH12768200.3 UIX-05025 FH12768200.3 UIX-05025Table 8. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters(Å2x103) for 10631ds. U(eq) is defined as one third of the trace of the orthogonalized Uijtensor. ______________________________________________________________________________ x y z U(eq) ______________________________________________________________________________ Br(1) 7291(2) -4827(6) 5651(2) 78(1) O(1) 4135(3) 6803(10) 2550(3) 42(1) O(2) 4408(4) 8547(13) 1912(4) 60(2) O(3) 2599(3) 7852(11) 3124(4) 46(2) O(4) 3359(3) 6564(10) 3025(5) 39(1) O(5) 5422(3) 944(12) 4309(4) 58(2) O(6) 5853(4) -248(15) 5052(4) 76(2) N(1) 3862(3) 9356(11) 3071(3) 40(1) N(2) 5956(5) -1376(19) 4215(5) 57(2) C(1) 4173(5) 8419(13) 2294(4) 46(1) C(2) 3818(4) 9843(12) 2470(4) 47(1) C(3) 3374(3) 9620(11) 3334(3) 40(1) C(4) 3057(3) 7997(13) 3131(4) 40(1) C(5) 3983(5) 11837(15) 2356(6) 63(2) C(6) 3291(5) 9443(17) 2120(5) 61(2) C(7) 3493(4) 9469(12) 3947(3) 41(2) C(8) 3096(4) 11503(13) 3201(4) 48(2) C(9) 4323(4) 10236(13) 3385(4) 49(2) C(10) 4283(3) 5975(10) 3541(3) 40(1) C(11) 4074(2) 5073(11) 3952(3) 41(1) C(12) 4383(3) 3952(10) 4318(3) 46(1) C(13) 4903(2) 3732(10) 4274(3) 52(1) C(14) 5112(2) 4634(11) 3863(3) 52(1) C(15) 4802(3) 5755(10) 3496(3) 49(1) C(16) 5252(5) 2436(15) 4647(4) 57(2) C(17) 5758(5) -231(16) 4567(4) 59(2) C(18) 6353(7) -2700(20) 4331(4) 55(1) C(19) 6617(7) -3000(20) 4848(4) 57(2) C(20) 6977(6) -4431(19) 4938(3) 56(2) C(21) 7074(5) -5559(17) 4511(3) 56(2) FH12768200.3 UIX-05025 C(22) 6810(5) -5260(18) 3994(3) 57(2) C(23) 6450(6) -3830(20) 3904(3) 55(2) B(1) 3910(4) 7050(14) 3063(4) 39(1) Br(1A) 7368(2) -4660(7) 5758(2) 54(1) O(1A) 4035(5) 7131(15) 2499(5) 41(1) O(2A) 4298(5) 9237(16) 1947(5) 51(2) O(3A) 2577(4) 7069(18) 3164(6) 52(2) O(4A) 3378(5) 6159(15) 3055(7) 39(1) O(5A) 5591(5) 1278(16) 4252(5) 56(2) O(6A) 6118(5) 479(17) 5017(5) 63(3) N(1A) 3744(4) 9251(15) 3148(4) 41(1) N(2A) 6059(7) -1270(30) 4240(7) 57(2) C(1A) 4127(7) 8915(17) 2367(5) 45(1) C(2A) 4086(5) 10223(14) 2809(5) 45(1) C(3A) 3157(4) 9242(15) 2905(5) 43(1) C(4A) 3007(5) 7411(18) 3098(6) 41(1) C(5A) 4628(5) 10417(19) 3147(6) 53(3) C(6A) 3936(7) 12194(18) 2614(7) 54(3) C(7A) 2872(7) 10850(20) 3119(7) 56(3) C(8A) 3039(7) 9170(20) 2270(5) 57(3) C(9A) 3796(5) 9711(18) 3730(5) 47(2) C(10A) 4305(4) 5887(15) 3461(4) 41(1) C(11A) 4196(3) 5287(16) 3962(4) 42(1) C(12A) 4567(4) 4323(15) 4309(3) 45(1) C(13A) 5046(3) 3959(15) 4155(3) 49(1) C(14A) 5155(3) 4559(15) 3654(4) 49(2) C(15A) 4784(4) 5523(15) 3307(3) 44(2) C(16A) 5457(6) 2950(20) 4547(5) 53(2) C(17A) 5945(7) 190(20) 4548(6) 59(2) C(18A) 6398(9) -2770(30) 4413(6) 56(1) C(19A) 6649(10) -2970(30) 4940(5) 57(2) C(20A) 7029(8) -4320(30) 5057(4) 57(2) C(21A) 7157(7) -5470(20) 4648(5) 56(2) C(22A) 6906(7) -5270(30) 4122(5) 57(2) C(23A) 6527(8) -3910(30) 4004(5) 56(2) FH12768200.3 UIX-05025 B(1A) 3887(5) 7033(18) 3053(6) 40(1) Table 9. Bond lengths [Å] and angles [°] for 10631ds. _____________________________________________________ Br(1)-C(20) 1.870(6) O(1)-C(1) 1.335(10) O(1)-B(1) 1.492(10) O(2)-C(1) 1.209(10) O(3)-C(4) 1.203(10) O(4)-C(4) 1.346(10) O(4)-B(1) 1.477(10) O(5)-C(17) 1.320(11) O(5)-C(16) 1.472(10) O(6)-C(17) 1.199(11) N(1)-C(9) 1.484(11) N(1)-C(2) 1.529(11) N(1)-C(3) 1.529(10) N(1)-B(1) 1.661(10) N(2)-C(17) 1.357(11) N(2)-C(18) 1.412(9) N(2)-H(2) 0.8800 C(1)-C(2) 1.491(12) C(2)-C(5) 1.534(13) C(2)-C(6) 1.551(14) C(3)-C(4) 1.477(12) C(3)-C(7) 1.522(11) C(3)-C(8) 1.549(11) C(5)-H(5A) 0.9800 C(5)-H(5B) 0.9800 C(5)-H(5C) 0.9800 C(6)-H(6A) 0.9800 C(6)-H(6B) 0.9800 C(6)-H(6C) 0.9800 C(7)-H(7A) 0.9800 C(7)-H(7B) 0.9800 FH12768200.3 UIX-05025 C(7)-H(7C) 0.9800 C(8)-H(8A) 0.9800 C(8)-H(8B) 0.9800 C(8)-H(8C) 0.9800 C(9)-H(9A) 0.9800 C(9)-H(9B) 0.9800 C(9)-H(9C) 0.9800 C(10)-C(11) 1.3900 C(10)-C(15) 1.3900 C(10)-B(1) 1.625(9) C(11)-C(12) 1.3900 C(11)-H(11) 0.9500 C(12)-C(13) 1.3900 C(12)-H(12) 0.9500 C(13)-C(14) 1.3900 C(13)-C(16) 1.527(9) C(14)-C(15) 1.3900 C(14)-H(14) 0.9500 C(15)-H(15) 0.9500 C(16)-H(16A) 0.9900 C(16)-H(16B) 0.9900 C(18)-C(19) 1.3900 C(18)-C(23) 1.3900 C(19)-C(20) 1.3900 C(19)-H(19) 0.9500 C(20)-C(21) 1.3900 C(21)-C(22) 1.3900 C(21)-H(21) 0.9500 C(22)-C(23) 1.3900 C(22)-H(22) 0.9500 C(23)-H(23) 0.9500 Br(1A)-C(20A) 1.862(9) O(1A)-C(1A) 1.353(13) O(1A)-B(1A) 1.488(12) O(2A)-C(1A) 1.220(13) O(3A)-C(4A) 1.189(12) FH12768200.3 UIX-05025 O(4A)-C(4A) 1.339(13) O(4A)-B(1A) 1.477(13) O(5A)-C(17A) 1.348(13) O(5A)-C(16A) 1.476(13) O(6A)-C(17A) 1.209(14) N(1A)-C(9A) 1.476(13) N(1A)-C(2A) 1.491(13) N(1A)-C(3A) 1.569(14) N(1A)-B(1A) 1.662(12) N(2A)-C(17A) 1.362(14) N(2A)-C(18A) 1.421(12) N(2A)-H(2A) 0.8800 C(1A)-C(2A) 1.465(15) C(2A)-C(6A) 1.530(15) C(2A)-C(5A) 1.552(16) C(3A)-C(4A) 1.474(14) C(3A)-C(7A) 1.515(15) C(3A)-C(8A) 1.569(15) C(5A)-H(5D) 0.9800 C(5A)-H(5E) 0.9800 C(5A)-H(5F) 0.9800 C(6A)-H(6D) 0.9800 C(6A)-H(6E) 0.9800 C(6A)-H(6F) 0.9800 C(7A)-H(7D) 0.9800 C(7A)-H(7E) 0.9800 C(7A)-H(7F) 0.9800 C(8A)-H(8D) 0.9800 C(8A)-H(8E) 0.9800 C(8A)-H(8F) 0.9800 C(9A)-H(9D) 0.9800 C(9A)-H(9E) 0.9800 C(9A)-H(9F) 0.9800 C(10A)-C(11A) 1.3900 C(10A)-C(15A) 1.3900 C(10A)-B(1A) 1.611(11) FH12768200.3 UIX-05025 C(11A)-C(12A) 1.3900 C(11A)-H(11A) 0.9500 C(12A)-C(13A) 1.3900 C(12A)-H(12A) 0.9500 C(13A)-C(14A) 1.3900 C(13A)-C(16A) 1.530(11) C(14A)-C(15A) 1.3900 C(14A)-H(14A) 0.9500 C(15A)-H(15A) 0.9500 C(16A)-H(16C) 0.9900 C(16A)-H(16D) 0.9900 C(18A)-C(19A) 1.3900 C(18A)-C(23A) 1.3900 C(19A)-C(20A) 1.3900 C(19A)-H(19A) 0.9500 C(20A)-C(21A) 1.3900 C(21A)-C(22A) 1.3900 C(21A)-H(21A) 0.9500 C(22A)-C(23A) 1.3900 C(22A)-H(22A) 0.9500 C(23A)-H(23A) 0.9500 C(1)-O(1)-B(1) 111.9(7) C(4)-O(4)-B(1) 113.7(7) C(17)-O(5)-C(16) 114.9(8) C(9)-N(1)-C(2) 111.1(7) C(9)-N(1)-C(3) 112.9(7) C(2)-N(1)-C(3) 116.2(7) C(9)-N(1)-B(1) 111.9(7) C(2)-N(1)-B(1) 102.1(6) C(3)-N(1)-B(1) 101.5(6) C(17)-N(2)-C(18) 128.0(10) C(17)-N(2)-H(2) 116.0 C(18)-N(2)-H(2) 116.0 O(2)-C(1)-O(1) 121.6(9) O(2)-C(1)-C(2) 126.1(9) O(1)-C(1)-C(2) 111.2(7) FH12768200.3 UIX-05025 C(1)-C(2)-N(1) 99.8(7) C(1)-C(2)-C(5) 112.4(8) N(1)-C(2)-C(5) 114.4(8) C(1)-C(2)-C(6) 104.5(9) N(1)-C(2)-C(6) 116.5(8) C(5)-C(2)-C(6) 108.6(9) C(4)-C(3)-C(7) 108.2(7) C(4)-C(3)-N(1) 102.6(6) C(7)-C(3)-N(1) 110.9(7) C(4)-C(3)-C(8) 113.1(8) C(7)-C(3)-C(8) 107.5(7) N(1)-C(3)-C(8) 114.4(7) O(3)-C(4)-O(4) 122.9(9) O(3)-C(4)-C(3) 125.7(8) O(4)-C(4)-C(3) 110.8(7) C(2)-C(5)-H(5A) 109.5 C(2)-C(5)-H(5B) 109.5 H(5A)-C(5)-H(5B) 109.5 C(2)-C(5)-H(5C) 109.5 H(5A)-C(5)-H(5C) 109.5 H(5B)-C(5)-H(5C) 109.5 C(2)-C(6)-H(6A) 109.5 C(2)-C(6)-H(6B) 109.5 H(6A)-C(6)-H(6B) 109.5 C(2)-C(6)-H(6C) 109.5 H(6A)-C(6)-H(6C) 109.5 H(6B)-C(6)-H(6C) 109.5 C(3)-C(7)-H(7A) 109.5 C(3)-C(7)-H(7B) 109.5 H(7A)-C(7)-H(7B) 109.5 C(3)-C(7)-H(7C) 109.5 H(7A)-C(7)-H(7C) 109.5 H(7B)-C(7)-H(7C) 109.5 C(3)-C(8)-H(8A) 109.5 C(3)-C(8)-H(8B) 109.5 H(8A)-C(8)-H(8B) 109.5 FH12768200.3 UIX-05025 C(3)-C(8)-H(8C) 109.5 H(8A)-C(8)-H(8C) 109.5 H(8B)-C(8)-H(8C) 109.5 N(1)-C(9)-H(9A) 109.5 N(1)-C(9)-H(9B) 109.5 H(9A)-C(9)-H(9B) 109.5 N(1)-C(9)-H(9C) 109.5 H(9A)-C(9)-H(9C) 109.5 H(9B)-C(9)-H(9C) 109.5 C(11)-C(10)-C(15) 120.0 C(11)-C(10)-B(1) 120.2(5) C(15)-C(10)-B(1) 119.2(5) C(12)-C(11)-C(10) 120.0 C(12)-C(11)-H(11) 120.0 C(10)-C(11)-H(11) 120.0 C(13)-C(12)-C(11) 120.0 C(13)-C(12)-H(12) 120.0 C(11)-C(12)-H(12) 120.0 C(12)-C(13)-C(14) 120.0 C(12)-C(13)-C(16) 122.0(6) C(14)-C(13)-C(16) 117.9(6) C(15)-C(14)-C(13) 120.0 C(15)-C(14)-H(14) 120.0 C(13)-C(14)-H(14) 120.0 C(14)-C(15)-C(10) 120.0 C(14)-C(15)-H(15) 120.0 C(10)-C(15)-H(15) 120.0 O(5)-C(16)-C(13) 107.3(7) O(5)-C(16)-H(16A) 110.3 C(13)-C(16)-H(16A) 110.3 O(5)-C(16)-H(16B) 110.3 C(13)-C(16)-H(16B) 110.3 H(16A)-C(16)-H(16B) 108.5 O(6)-C(17)-O(5) 121.7(9) O(6)-C(17)-N(2) 127.0(10) O(5)-C(17)-N(2) 111.2(9) FH12768200.3 UIX-05025 C(19)-C(18)-C(23) 120.0 C(19)-C(18)-N(2) 123.2(7) C(23)-C(18)-N(2) 116.6(7) C(18)-C(19)-C(20) 120.0 C(18)-C(19)-H(19) 120.0 C(20)-C(19)-H(19) 120.0 C(21)-C(20)-C(19) 120.0 C(21)-C(20)-Br(1) 122.4(5) C(19)-C(20)-Br(1) 117.6(5) C(20)-C(21)-C(22) 120.0 C(20)-C(21)-H(21) 120.0 C(22)-C(21)-H(21) 120.0 C(23)-C(22)-C(21) 120.0 C(23)-C(22)-H(22) 120.0 C(21)-C(22)-H(22) 120.0 C(22)-C(23)-C(18) 120.0 C(22)-C(23)-H(23) 120.0 C(18)-C(23)-H(23) 120.0 O(4)-B(1)-O(1) 114.8(9) O(4)-B(1)-C(10) 114.5(7) O(1)-B(1)-C(10) 107.6(7) O(4)-B(1)-N(1) 99.2(6) O(1)-B(1)-N(1) 99.8(6) C(10)-B(1)-N(1) 120.2(8) C(1A)-O(1A)-B(1A) 110.5(10) C(4A)-O(4A)-B(1A) 112.4(10) C(17A)-O(5A)-C(16A) 113.0(10) C(9A)-N(1A)-C(2A) 118.3(10) C(9A)-N(1A)-C(3A) 109.3(9) C(2A)-N(1A)-C(3A) 114.6(9) C(9A)-N(1A)-B(1A) 111.4(9) C(2A)-N(1A)-B(1A) 101.6(8) C(3A)-N(1A)-B(1A) 99.8(8) C(17A)-N(2A)-C(18A) 126.2(13) C(17A)-N(2A)-H(2A) 116.9 C(18A)-N(2A)-H(2A) 116.9 FH12768200.3 UIX-05025 O(2A)-C(1A)-O(1A) 119.3(12) O(2A)-C(1A)-C(2A) 127.0(11) O(1A)-C(1A)-C(2A) 112.9(10) C(1A)-C(2A)-N(1A) 104.0(9) C(1A)-C(2A)-C(6A) 113.3(11) N(1A)-C(2A)-C(6A) 117.8(11) C(1A)-C(2A)-C(5A) 107.8(11) N(1A)-C(2A)-C(5A) 108.2(10) C(6A)-C(2A)-C(5A) 105.2(10) C(4A)-C(3A)-C(7A) 113.3(11) C(4A)-C(3A)-N(1A) 99.7(9) C(7A)-C(3A)-N(1A) 111.5(10) C(4A)-C(3A)-C(8A) 106.0(11) C(7A)-C(3A)-C(8A) 110.3(11) N(1A)-C(3A)-C(8A) 115.6(10) O(3A)-C(4A)-O(4A) 125.9(12) O(3A)-C(4A)-C(3A) 122.2(12) O(4A)-C(4A)-C(3A) 110.0(9) C(2A)-C(5A)-H(5D) 109.5 C(2A)-C(5A)-H(5E) 109.5 H(5D)-C(5A)-H(5E) 109.5 C(2A)-C(5A)-H(5F) 109.5 H(5D)-C(5A)-H(5F) 109.5 H(5E)-C(5A)-H(5F) 109.5 C(2A)-C(6A)-H(6D) 109.5 C(2A)-C(6A)-H(6E) 109.5 H(6D)-C(6A)-H(6E) 109.5 C(2A)-C(6A)-H(6F) 109.5 H(6D)-C(6A)-H(6F) 109.5 H(6E)-C(6A)-H(6F) 109.5 C(3A)-C(7A)-H(7D) 109.5 C(3A)-C(7A)-H(7E) 109.5 H(7D)-C(7A)-H(7E) 109.5 C(3A)-C(7A)-H(7F) 109.5 H(7D)-C(7A)-H(7F) 109.5 H(7E)-C(7A)-H(7F) 109.5 FH12768200.3 UIX-05025 C(3A)-C(8A)-H(8D) 109.5 C(3A)-C(8A)-H(8E) 109.5 H(8D)-C(8A)-H(8E) 109.5 C(3A)-C(8A)-H(8F) 109.5 H(8D)-C(8A)-H(8F) 109.5 H(8E)-C(8A)-H(8F) 109.5 N(1A)-C(9A)-H(9D) 109.5 N(1A)-C(9A)-H(9E) 109.5 H(9D)-C(9A)-H(9E) 109.5 N(1A)-C(9A)-H(9F) 109.5 H(9D)-C(9A)-H(9F) 109.5 H(9E)-C(9A)-H(9F) 109.5 C(11A)-C(10A)-C(15A) 120.0 C(11A)-C(10A)-B(1A) 121.3(7) C(15A)-C(10A)-B(1A) 118.7(7) C(10A)-C(11A)-C(12A) 120.0 C(10A)-C(11A)-H(11A) 120.0 C(12A)-C(11A)-H(11A) 120.0 C(13A)-C(12A)-C(11A) 120.0 C(13A)-C(12A)-H(12A) 120.0 C(11A)-C(12A)-H(12A) 120.0 C(12A)-C(13A)-C(14A) 120.0 C(12A)-C(13A)-C(16A) 119.5(8) C(14A)-C(13A)-C(16A) 120.4(8) C(15A)-C(14A)-C(13A) 120.0 C(15A)-C(14A)-H(14A) 120.0 C(13A)-C(14A)-H(14A) 120.0 C(14A)-C(15A)-C(10A) 120.0 C(14A)-C(15A)-H(15A) 120.0 C(10A)-C(15A)-H(15A) 120.0 O(5A)-C(16A)-C(13A) 105.2(9) O(5A)-C(16A)-H(16C) 110.7 C(13A)-C(16A)-H(16C) 110.7 O(5A)-C(16A)-H(16D) 110.7 C(13A)-C(16A)-H(16D) 110.7 H(16C)-C(16A)-H(16D) 108.8 FH12768200.3 UIX-05025 O(6A)-C(17A)-O(5A) 124.4(12) O(6A)-C(17A)-N(2A) 126.5(12) O(5A)-C(17A)-N(2A) 109.1(11) C(19A)-C(18A)-C(23A) 120.0 C(19A)-C(18A)-N(2A) 123.9(9) C(23A)-C(18A)-N(2A) 115.6(9) C(20A)-C(19A)-C(18A) 120.0 C(20A)-C(19A)-H(19A) 120.0 C(18A)-C(19A)-H(19A) 120.0 C(21A)-C(20A)-C(19A) 120.0 C(21A)-C(20A)-Br(1A) 118.6(7) C(19A)-C(20A)-Br(1A) 121.4(7) C(22A)-C(21A)-C(20A) 120.0 C(22A)-C(21A)-H(21A) 120.0 C(20A)-C(21A)-H(21A) 120.0 C(21A)-C(22A)-C(23A) 120.0 C(21A)-C(22A)-H(22A) 120.0 C(23A)-C(22A)-H(22A) 120.0 C(22A)-C(23A)-C(18A) 120.0 C(22A)-C(23A)-H(23A) 120.0 C(18A)-C(23A)-H(23A) 120.0 O(4A)-B(1A)-O(1A) 112.3(12) O(4A)-B(1A)-C(10A) 108.3(9) O(1A)-B(1A)-C(10A) 111.6(9) O(4A)-B(1A)-N(1A) 100.6(8) O(1A)-B(1A)-N(1A) 100.5(8) C(10A)-B(1A)-N(1A) 123.1(10) _____________________________________________________________ Symmetry transformations used to generate equivalent atomsTable 10. Anisotropic displacement parameters (Å2x 103) for 10631ds.The anisotropic displacement factor exponent takes the form: -2p2[ h2a*2U11+ ... + 2 h k a*b* U12].______________________________________________________________________________ U11U22U33U23U13U12FH12768200.3 UIX-05025 ______________________________________________________________________________ Br(1) 93(2) 84(2) 55(1) 3(1) -1(1) 50(2) O(1) 55(3) 29(2) 46(2) 3(2) 20(2) 4(2) O(2) 81(4) 46(4) 63(4) 16(4) 39(3) 19(4) O(3) 45(3) 34(3) 60(3) -3(3) 6(3) -5(3) O(4) 47(2) 26(2) 43(2) -5(2) 8(2) -6(2) O(5) 67(3) 53(3) 53(2) -10(2) 3(3) 22(3) O(6) 91(5) 76(5) 57(4) -4(4) 1(4) 42(4) N(1) 48(2) 27(2) 48(2) 0(2) 16(2) 0(2) N(2) 67(3) 53(2) 52(2) -3(2) 7(3) 22(3) C(1) 59(3) 32(3) 51(2) 6(2) 20(2) 7(2) C(2) 61(2) 32(2) 50(2) 5(2) 19(2) 3(2) C(3) 46(2) 29(2) 46(2) -2(2) 12(2) -1(2) C(4) 46(2) 29(3) 46(2) -2(2) 10(2) -2(2) C(5) 85(5) 39(4) 70(5) 7(4) 33(5) 6(4) C(6) 74(6) 58(5) 53(5) 9(4) 13(4) 16(5) C(7) 47(4) 31(4) 47(4) -5(3) 10(3) -4(3) C(8) 55(4) 29(4) 62(4) -3(4) 13(4) 2(3) C(9) 51(4) 33(3) 66(4) -5(3) 16(3) -7(3) C(10) 48(2) 30(2) 44(2) -6(2) 10(2) 4(2) C(11) 50(3) 32(2) 41(2) -6(2) 7(2) 7(2) C(12) 55(3) 39(3) 43(2) -6(2) 6(2) 11(2) C(13) 60(3) 46(2) 49(2) -5(2) 5(2) 15(2) C(14) 57(3) 47(2) 52(3) -3(2) 9(3) 11(2) C(15) 54(2) 41(2) 51(3) -3(3) 10(3) 6(2) C(16) 64(3) 51(3) 53(3) -7(2) 3(3) 22(3) C(17) 70(3) 56(3) 51(2) -4(2) 5(3) 22(3) C(18) 65(3) 52(2) 50(3) 2(2) 11(3) 18(2) C(19) 67(3) 53(2) 52(3) 3(3) 13(3) 21(2) C(20) 66(3) 54(3) 50(3) 7(3) 12(3) 20(3) C(21) 66(3) 52(3) 51(4) 6(3) 14(3) 20(3) C(22) 67(4) 54(3) 51(3) 4(3) 13(3) 21(3) C(23) 65(4) 53(3) 50(3) 3(3) 12(3) 18(3) B(1) 48(2) 27(2) 44(2) -1(2) 13(2) 0(2) Br(1A) 50(1) 55(1) 57(2) 13(1) 11(1) 10(1) O(1A) 54(3) 28(3) 44(2) 2(2) 15(2) 4(2) FH12768200.3 UIX-05025 O(2A) 72(5) 36(4) 51(4) 1(4) 22(4) 1(4) O(3A) 45(4) 54(5) 56(4) 6(5) 5(3) -7(5) O(4A) 46(2) 28(3) 43(2) -1(2) 9(2) -4(2) O(5A) 65(3) 51(3) 50(3) -8(2) 5(3) 21(3) O(6A) 80(6) 54(5) 52(4) -10(4) -5(5) 24(4) N(1A) 51(2) 28(2) 46(2) 0(2) 13(2) 0(2) N(2A) 67(3) 53(3) 52(3) -2(2) 7(3) 20(3) C(1A) 60(3) 31(3) 49(2) 4(2) 19(2) 4(2) C(2A) 58(2) 30(2) 51(2) 3(2) 17(2) 1(2) C(3A) 50(2) 32(2) 49(2) -2(2) 11(2) 0(2) C(4A) 47(2) 31(3) 46(2) 1(3) 9(2) -3(2) C(5A) 63(6) 39(5) 59(6) -5(5) 12(5) -6(5) C(6A) 78(5) 32(5) 53(5) 1(5) 17(5) 0(5) C(7A) 63(6) 48(5) 58(5) -2(5) 12(5) 10(5) C(8A) 64(6) 49(6) 55(6) 4(5) 2(5) 4(6) C(9A) 56(4) 36(4) 50(4) -5(4) 11(4) 3(4) C(10A) 50(2) 31(2) 43(2) -4(2) 10(2) 3(2) C(11A) 51(3) 34(3) 42(2) -6(2) 8(3) 8(2) C(12A) 54(3) 39(3) 43(2) -5(2) 9(3) 11(2) C(13A) 57(3) 45(2) 45(3) -6(2) 8(3) 15(2) C(14A) 57(3) 46(3) 45(3) -7(3) 10(3) 11(2) C(15A) 52(3) 38(3) 44(3) -7(3) 10(3) 8(2) C(16A) 62(3) 48(3) 49(3) -7(3) 5(3) 18(3) C(17A) 68(3) 54(3) 52(2) -4(2) 4(3) 21(3) C(18A) 65(3) 52(2) 51(3) 2(3) 11(3) 19(2) C(19A) 67(3) 53(3) 52(3) 3(3) 13(3) 20(3) C(20A) 65(3) 54(3) 53(3) 6(3) 14(3) 20(3) C(21A) 65(4) 53(3) 51(4) 7(3) 12(3) 19(3) C(22A) 66(4) 53(3) 52(4) 3(3) 12(3) 20(3) C(23A) 65(4) 53(3) 51(3) 3(3) 11(3) 18(3) B(1A) 49(2) 28(2) 44(2) -1(2) 13(2) 0(2) ______________________________________________________________________________Table 11. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x103)for 10631ds. ______________________________________________________________________________ FH12768200.3 UIX-05025 U(eq) ______________________________________________________________________________ H(2) 5819 -1278 3873 86 H(5A) 4005 11971 1969 94 H(5B) 4320 12095 2567 94 H(5C) 3728 12717 2459 94 H(6A) 3330 9523 1735 92 H(6B) 3037 10363 2202 92 H(6C) 3174 8192 2201 92 H(7A) 3689 8325 4044 62 H(7B) 3170 9435 4102 62 H(7C) 3697 10548 4091 62 H(8A) 2951 11535 2817 72 H(8B) 3343 12524 3281 72 H(8C) 2817 11640 3422 72 H(9A) 4625 9990 3206 74 H(9B) 4379 9717 3752 74 H(9C) 4268 11583 3404 74 H(11) 3719 5224 3982 50 H(12) 4240 3336 4599 55 H(14) 5467 4483 3833 62 H(15) 4945 6371 3215 58 H(16A) 5554 3129 4832 68 H(16B) 5062 1903 4927 68 H(19) 6551 -2232 5140 68 H(21) 7320 -6535 4573 67 H(22) 6876 -6032 3703 68 H(23) 6270 -3628 3551 66 H(2A) 5909 -1296 3901 86 H(5D) 4726 9237 3331 80 H(5E) 4622 11404 3417 80 H(5F) 4880 10733 2907 80 H(6D) 4224 12765 2463 81 H(6E) 3855 12942 2919 81 H(6F) 3633 12137 2334 81 H(7D) 3038 12025 3044 84 FH12768200.3 UIX-05025 H(7E) 2880 10710 3511 84 H(7F) 2513 10854 2942 84 H(8D) 3127 7932 2144 85 H(8E) 3244 10114 2115 85 H(8F) 2671 9407 2155 85 H(9D) 3760 11059 3774 71 H(9E) 4136 9312 3909 71 H(9F) 3527 9069 3894 71 H(11A) 3869 5536 4068 51 H(12A) 4493 3913 4652 54 H(14A) 5482 4311 3548 59 H(15A) 4858 5934 2964 53 H(16C) 5764 3751 4644 64 H(16D) 5319 2596 4882 64 H(19A) 6561 -2186 5219 68 H(21A) 7416 -6391 4729 67 H(22A) 6994 -6050 3842 68 H(23A) 6356 -3776 3644 67 Table 12. Torsion angles [°] for 10631ds. ________________________________________________________________ B(1)-O(1)-C(1)-O(2) 169.8(11) B(1)-O(1)-C(1)-C(2) -20.9(13) O(2)-C(1)-C(2)-N(1) -153.9(12) O(1)-C(1)-C(2)-N(1) 37.4(11) O(2)-C(1)-C(2)-C(5) -32.3(17) O(1)-C(1)-C(2)-C(5) 159.0(10) O(2)-C(1)-C(2)-C(6) 85.3(14) O(1)-C(1)-C(2)-C(6) -83.4(11) C(9)-N(1)-C(2)-C(1) 83.2(9) C(3)-N(1)-C(2)-C(1) -145.9(8) B(1)-N(1)-C(2)-C(1) -36.4(8) C(9)-N(1)-C(2)-C(5) -37.0(11) C(3)-N(1)-C(2)-C(5) 94.0(10) B(1)-N(1)-C(2)-C(5) -156.5(8) FH12768200.3 UIX-05025 C(9)-N(1)-C(2)-C(6) -165.2(8) C(3)-N(1)-C(2)-C(6) -34.2(10) B(1)-N(1)-C(2)-C(6) 75.3(9) C(9)-N(1)-C(3)-C(4) -153.8(8) C(2)-N(1)-C(3)-C(4) 76.0(9) B(1)-N(1)-C(3)-C(4) -33.8(8) C(9)-N(1)-C(3)-C(7) -38.5(9) C(2)-N(1)-C(3)-C(7) -168.6(7) B(1)-N(1)-C(3)-C(7) 81.6(8) C(9)-N(1)-C(3)-C(8) 83.3(9) C(2)-N(1)-C(3)-C(8) -46.8(10) B(1)-N(1)-C(3)-C(8) -156.7(8) B(1)-O(4)-C(4)-O(3) -179.3(11) B(1)-O(4)-C(4)-C(3) -8.1(13) C(7)-C(3)-C(4)-O(3) 81.6(12) N(1)-C(3)-C(4)-O(3) -161.1(11) C(8)-C(3)-C(4)-O(3) -37.3(14) C(7)-C(3)-C(4)-O(4) -89.3(10) N(1)-C(3)-C(4)-O(4) 27.9(10) C(8)-C(3)-C(4)-O(4) 151.7(9) C(15)-C(10)-C(11)-C(12) 0.0 B(1)-C(10)-C(11)-C(12) 171.5(7) C(10)-C(11)-C(12)-C(13) 0.0 C(11)-C(12)-C(13)-C(14) 0.0 C(11)-C(12)-C(13)-C(16) -176.7(8) C(12)-C(13)-C(14)-C(15) 0.0 C(16)-C(13)-C(14)-C(15) 176.8(7) C(13)-C(14)-C(15)-C(10) 0.0 C(11)-C(10)-C(15)-C(14) 0.0 B(1)-C(10)-C(15)-C(14) -171.6(7) C(17)-O(5)-C(16)-C(13) 175.5(10) C(12)-C(13)-C(16)-O(5) 115.6(8) C(14)-C(13)-C(16)-O(5) -61.2(10) C(16)-O(5)-C(17)-O(6) 11.3(19) C(16)-O(5)-C(17)-N(2) -170.3(12) C(18)-N(2)-C(17)-O(6) -7(3) FH12768200.3 UIX-05025 C(18)-N(2)-C(17)-O(5) 174.4(16) C(17)-N(2)-C(18)-C(19) -1(2) C(17)-N(2)-C(18)-C(23) 173.8(14) C(23)-C(18)-C(19)-C(20) 0.0 N(2)-C(18)-C(19)-C(20) 175.1(17) C(18)-C(19)-C(20)-C(21) 0.0 C(18)-C(19)-C(20)-Br(1) -176.9(11) C(19)-C(20)-C(21)-C(22) 0.0 Br(1)-C(20)-C(21)-C(22) 176.7(11) C(20)-C(21)-C(22)-C(23) 0.0 C(21)-C(22)-C(23)-C(18) 0.0 C(19)-C(18)-C(23)-C(22) 0.0 N(2)-C(18)-C(23)-C(22) -175.5(16) C(4)-O(4)-B(1)-O(1) -119.1(10) C(4)-O(4)-B(1)-C(10) 115.6(10) C(4)-O(4)-B(1)-N(1) -13.8(11) C(1)-O(1)-B(1)-O(4) 100.9(10) C(1)-O(1)-B(1)-C(10) -130.4(9) C(1)-O(1)-B(1)-N(1) -4.2(10) C(11)-C(10)-B(1)-O(4) -15.5(10) C(15)-C(10)-B(1)-O(4) 156.1(7) C(11)-C(10)-B(1)-O(1) -144.4(6) C(15)-C(10)-B(1)-O(1) 27.2(9) C(11)-C(10)-B(1)-N(1) 102.5(8) C(15)-C(10)-B(1)-N(1) -85.9(8) C(9)-N(1)-B(1)-O(4) 149.7(8) C(2)-N(1)-B(1)-O(4) -91.3(8) C(3)-N(1)-B(1)-O(4) 29.0(9) C(9)-N(1)-B(1)-O(1) -93.0(8) C(2)-N(1)-B(1)-O(1) 26.0(8) C(3)-N(1)-B(1)-O(1) 146.3(7) C(9)-N(1)-B(1)-C(10) 24.2(11) C(2)-N(1)-B(1)-C(10) 143.2(8) C(3)-N(1)-B(1)-C(10) -96.5(8) B(1A)-O(1A)-C(1A)-O(2A) 173.4(15) B(1A)-O(1A)-C(1A)-C(2A) 3.4(17) FH12768200.3 UIX-05025 O(2A)-C(1A)-C(2A)-N(1A) 167.1(16) O(1A)-C(1A)-C(2A)-N(1A) -23.8(16) O(2A)-C(1A)-C(2A)-C(6A) 38(2) O(1A)-C(1A)-C(2A)-C(6A) -153.0(13) O(2A)-C(1A)-C(2A)-C(5A) -78(2) O(1A)-C(1A)-C(2A)-C(5A) 90.9(14) C(9A)-N(1A)-C(2A)-C(1A) 153.3(11) C(3A)-N(1A)-C(2A)-C(1A) -75.5(12) B(1A)-N(1A)-C(2A)-C(1A) 31.1(12) C(9A)-N(1A)-C(2A)-C(6A) -80.3(14) C(3A)-N(1A)-C(2A)-C(6A) 50.9(14) B(1A)-N(1A)-C(2A)-C(6A) 157.5(11) C(9A)-N(1A)-C(2A)-C(5A) 38.8(13) C(3A)-N(1A)-C(2A)-C(5A) 170.1(9) B(1A)-N(1A)-C(2A)-C(5A) -83.4(10) C(9A)-N(1A)-C(3A)-C(4A) -78.5(11) C(2A)-N(1A)-C(3A)-C(4A) 146.1(10) B(1A)-N(1A)-C(3A)-C(4A) 38.4(10) C(9A)-N(1A)-C(3A)-C(7A) 41.5(13) C(2A)-N(1A)-C(3A)-C(7A) -94.0(12) B(1A)-N(1A)-C(3A)-C(7A) 158.4(10) C(9A)-N(1A)-C(3A)-C(8A) 168.4(11) C(2A)-N(1A)-C(3A)-C(8A) 33.0(13) B(1A)-N(1A)-C(3A)-C(8A) -74.6(11) B(1A)-O(4A)-C(4A)-O(3A) -171.8(16) B(1A)-O(4A)-C(4A)-C(3A) 23.7(17) C(7A)-C(3A)-C(4A)-O(3A) 36(2) N(1A)-C(3A)-C(4A)-O(3A) 154.4(14) C(8A)-C(3A)-C(4A)-O(3A) -85.2(17) C(7A)-C(3A)-C(4A)-O(4A) -159.0(13) N(1A)-C(3A)-C(4A)-O(4A) -40.4(14) C(8A)-C(3A)-C(4A)-O(4A) 80.0(14) C(15A)-C(10A)-C(11A)-C(12A) 0.0 B(1A)-C(10A)-C(11A)-C(12A) -179.1(11) C(10A)-C(11A)-C(12A)-C(13A) 0.0 C(11A)-C(12A)-C(13A)-C(14A) 0.0 FH12768200.3 UIX-05025 C(11A)-C(12A)-C(13A)-C(16A) 178.2(11) C(12A)-C(13A)-C(14A)-C(15A) 0.0 C(16A)-C(13A)-C(14A)-C(15A) -178.1(11) C(13A)-C(14A)-C(15A)-C(10A) 0.0 C(11A)-C(10A)-C(15A)-C(14A) 0.0 B(1A)-C(10A)-C(15A)-C(14A) 179.1(10) C(17A)-O(5A)-C(16A)-C(13A) -178.6(13) C(12A)-C(13A)-C(16A)-O(5A) 122.4(10) C(14A)-C(13A)-C(16A)-O(5A) -59.5(14) C(16A)-O(5A)-C(17A)-O(6A) 4(3) C(16A)-O(5A)-C(17A)-N(2A) -177.7(16) C(18A)-N(2A)-C(17A)-O(6A) 1(4) C(18A)-N(2A)-C(17A)-O(5A) -177(2) C(17A)-N(2A)-C(18A)-C(19A) 3(3) C(17A)-N(2A)-C(18A)-C(23A) -168.7(19) C(23A)-C(18A)-C(19A)-C(20A) 0.0 N(2A)-C(18A)-C(19A)-C(20A) -171(2) C(18A)-C(19A)-C(20A)-C(21A) 0.0 C(18A)-C(19A)-C(20A)-Br(1A) -179.2(16) C(19A)-C(20A)-C(21A)-C(22A) 0.0 Br(1A)-C(20A)-C(21A)-C(22A) 179.2(16) C(20A)-C(21A)-C(22A)-C(23A) 0.0 C(21A)-C(22A)-C(23A)-C(18A) 0.0 C(19A)-C(18A)-C(23A)-C(22A) 0.0 N(2A)-C(18A)-C(23A)-C(22A) 172(2) C(4A)-O(4A)-B(1A)-O(1A) -102.6(14) C(4A)-O(4A)-B(1A)-C(10A) 133.8(13) C(4A)-O(4A)-B(1A)-N(1A) 3.5(15) C(1A)-O(1A)-B(1A)-O(4A) 122.3(12) C(1A)-O(1A)-B(1A)-C(10A) -116.0(13) C(1A)-O(1A)-B(1A)-N(1A) 16.2(14) C(11A)-C(10A)-B(1A)-O(4A) -42.4(13) C(15A)-C(10A)-B(1A)-O(4A) 138.5(9) C(11A)-C(10A)-B(1A)-O(1A) -166.4(9) C(15A)-C(10A)-B(1A)-O(1A) 14.5(13) C(11A)-C(10A)-B(1A)-N(1A) 74.1(12) FH12768200.3 UIX-05025 C(15A)-C(10A)-B(1A)-N(1A) -105.0(11) C(9A)-N(1A)-B(1A)-O(4A) 88.9(12) C(2A)-N(1A)-B(1A)-O(4A) -144.3(11) C(3A)-N(1A)-B(1A)-O(4A) -26.5(11) C(9A)-N(1A)-B(1A)-O(1A) -155.9(10) C(2A)-N(1A)-B(1A)-O(1A) -29.0(11) C(3A)-N(1A)-B(1A)-O(1A) 88.8(10) C(9A)-N(1A)-B(1A)-C(10A) -31.3(14) C(2A)-N(1A)-B(1A)-C(10A) 95.6(12) C(3A)-N(1A)-B(1A)-C(10A) -146.6(10) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms Table 13. Hydrogen bonds for 10631ds [Å and °]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(2^a)-H(2^a)...O(2^a)#1 0.88 1.97 2.839(16) 169.6 N(2A^b)-H(2A^b)...O(2A^b)#1 0.88 2.14 3.00(2) 163.9 ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x+1,y-1,-z+1 / 2 Crystal data and structure refinement for 8 (10957ds), CCDC Number: 2293444 are provided below. Table 14. Crystal data and structure refinement for 10957ds. FH12768200.3 UIX-05025 Table 15. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters(Å2x103) for 10957d1s. U(eq) is defined as one third of the trace of the orthogonalized Uijtensor. ______________________________________________________________________________ FH12768200.3 UIX-05025 x y z U(eq) ______________________________________________________________________________ O(1) 8655(1) 1015(1) 6824(1) 24(1) O(2) 9641(1) 1372(1) 7375(1) 34(1) O(3) 8946(1) 581(1) 5219(1) 26(1) O(4) 8472(1) 578(1) 5937(1) 20(1) O(5) 4604(1) 2009(1) 6009(1) 22(1) O(6) 4454(1) 3957(1) 5672(1) 31(1) N(1) 8936(1) 2584(1) 6232(1) 18(1) N(2) 3921(1) 2195(1) 5302(1) 22(1) C(1) 9326(1) 1501(2) 6972(1) 24(1) C(2) 9663(1) 2152(2) 6550(1) 23(1) C(3) 8953(1) 2524(2) 5683(1) 20(1) C(4) 8805(1) 1122(2) 5584(1) 20(1) C(5) 10197(1) 3228(2) 6715(1) 32(1) C(6) 10121(1) 1083(2) 6336(1) 28(1) C(7) 8281(1) 3236(2) 5421(1) 24(1) C(8) 9661(1) 3021(2) 5484(1) 24(1) C(9) 8695(1) 3838(2) 6406(1) 24(1) C(10) 7462(1) 1772(1) 6344(1) 18(1) C(11) 6931(1) 1473(2) 5954(1) 20(1) C(12) 6164(1) 1699(2) 5966(1) 21(1) C(13) 5906(1) 2237(2) 6376(1) 20(1) C(14) 6423(1) 2533(2) 6772(1) 22(1) C(15) 7184(1) 2303(2) 6756(1) 22(1) C(16) 5082(1) 2508(2) 6416(1) 24(1) C(17) 4334(1) 2836(2) 5656(1) 21(1) C(18) 3561(1) 2650(2) 4857(1) 20(1) C(19) 3622(1) 3872(2) 4684(1) 21(1) C(20) 3278(1) 4186(2) 4224(1) 22(1) C(21) 2867(1) 3310(2) 3929(1) 20(1) C(22) 2799(1) 2097(2) 4113(1) 24(1) C(23) 3139(1) 1772(2) 4568(1) 25(1) C(24) 2519(1) 3624(2) 3430(1) 21(1) C(25) 2893(1) 4389(2) 3121(1) 24(1) C(26) 2576(1) 4655(2) 2651(1) 30(1) FH12768200.3 UIX-05025 C(27) 1877(1) 4181(2) 2485(1) 32(1) C(28) 1495(1) 3428(2) 2788(1) 32(1) C(29) 1815(1) 3145(2) 3255(1) 27(1) B(1) 8337(1) 1450(2) 6340(1) 19(1) ______________________________________________________________________________ FH12768200.3 UIX-05025 Table 16. Bond lengths [Å] and angles [°] for 10957d1s. _____________________________________________________ O(1)-C(1) 1.330(2) O(1)-B(1) 1.469(2) O(2)-C(1) 1.201(2) O(3)-C(4) 1.2076(19) O(4)-C(4) 1.3228(19) O(4)-B(1) 1.486(2) O(5)-C(17) 1.3617(19) O(5)-C(16) 1.4404(19) O(6)-C(17) 1.210(2) N(1)-C(9) 1.495(2) N(1)-C(3) 1.5205(19) N(1)-C(2) 1.5590(19) N(1)-B(1) 1.658(2) N(2)-C(17) 1.347(2) N(2)-C(18) 1.412(2) N(2)-H(2) 0.84(2) C(1)-C(2) 1.529(2) C(2)-C(5) 1.527(2) C(2)-C(6) 1.550(2) C(3)-C(8) 1.523(2) C(3)-C(4) 1.532(2) C(3)-C(7) 1.536(2) C(5)-H(5A) 0.9800 C(5)-H(5B) 0.9800 C(5)-H(5C) 0.9800 C(6)-H(6A) 0.9800 C(6)-H(6B) 0.9800 C(6)-H(6C) 0.9800 C(7)-H(7A) 0.9800 C(7)-H(7B) 0.9800 C(7)-H(7C) 0.9800 C(8)-H(8A) 0.9800 C(8)-H(8B) 0.9800 C(8)-H(8C) 0.9800 FH12768200.3 UIX-05025 C(9)-H(9A) 0.9800 C(9)-H(9B) 0.9800 C(9)-H(9C) 0.9800 C(10)-C(11) 1.396(2) C(10)-C(15) 1.404(2) C(10)-B(1) 1.601(2) C(11)-C(12) 1.395(2) C(11)-H(11) 0.9500 C(12)-C(13) 1.386(2) C(12)-H(12) 0.9500 C(13)-C(14) 1.394(2) C(13)-C(16) 1.516(2) C(14)-C(15) 1.386(2) C(14)-H(14) 0.9500 C(15)-H(15) 0.9500 C(16)-H(16A) 0.9900 C(16)-H(16B) 0.9900 C(18)-C(19) 1.392(2) C(18)-C(23) 1.397(2) C(19)-C(20) 1.391(2) C(19)-H(19) 0.9500 C(20)-C(21) 1.395(2) C(20)-H(20) 0.9500 C(21)-C(22) 1.395(2) C(21)-C(24) 1.487(2) C(22)-C(23) 1.380(2) C(22)-H(22) 0.9500 C(23)-H(23) 0.9500 C(24)-C(29) 1.396(2) C(24)-C(25) 1.397(2) C(25)-C(26) 1.387(2) C(25)-H(25) 0.9500 C(26)-C(27) 1.381(3) C(26)-H(26) 0.9500 C(27)-C(28) 1.386(3) C(27)-H(27) 0.9500 FH12768200.3 UIX-05025 C(28)-C(29) 1.387(2) C(28)-H(28) 0.9500 C(29)-H(29) 0.9500 C(1)-O(1)-B(1) 114.13(13) C(4)-O(4)-B(1) 113.37(12) C(17)-O(5)-C(16) 117.25(13) C(9)-N(1)-C(3) 113.16(12) C(9)-N(1)-C(2) 109.45(12) C(3)-N(1)-C(2) 116.57(11) C(9)-N(1)-B(1) 112.15(11) C(3)-N(1)-B(1) 103.12(11) C(2)-N(1)-B(1) 101.65(11) C(17)-N(2)-C(18) 128.63(14) C(17)-N(2)-H(2) 115.1(14) C(18)-N(2)-H(2) 116.1(14) O(2)-C(1)-O(1) 124.25(16) O(2)-C(1)-C(2) 124.80(15) O(1)-C(1)-C(2) 110.79(13) C(5)-C(2)-C(1) 113.27(14) C(5)-C(2)-C(6) 108.90(14) C(1)-C(2)-C(6) 102.77(14) C(5)-C(2)-N(1) 113.96(14) C(1)-C(2)-N(1) 100.93(12) C(6)-C(2)-N(1) 116.33(13) N(1)-C(3)-C(8) 116.44(13) N(1)-C(3)-C(4) 101.33(12) C(8)-C(3)-C(4) 114.13(13) N(1)-C(3)-C(7) 110.68(12) C(8)-C(3)-C(7) 107.39(13) C(4)-C(3)-C(7) 106.44(13) O(3)-C(4)-O(4) 123.51(15) O(3)-C(4)-C(3) 124.26(14) O(4)-C(4)-C(3) 112.16(13) C(2)-C(5)-H(5A) 109.5 C(2)-C(5)-H(5B) 109.5 H(5A)-C(5)-H(5B) 109.5 FH12768200.3 UIX-05025 C(2)-C(5)-H(5C) 109.5 H(5A)-C(5)-H(5C) 109.5 H(5B)-C(5)-H(5C) 109.5 C(2)-C(6)-H(6A) 109.5 C(2)-C(6)-H(6B) 109.5 H(6A)-C(6)-H(6B) 109.5 C(2)-C(6)-H(6C) 109.5 H(6A)-C(6)-H(6C) 109.5 H(6B)-C(6)-H(6C) 109.5 C(3)-C(7)-H(7A) 109.5 C(3)-C(7)-H(7B) 109.5 H(7A)-C(7)-H(7B) 109.5 C(3)-C(7)-H(7C) 109.5 H(7A)-C(7)-H(7C) 109.5 H(7B)-C(7)-H(7C) 109.5 C(3)-C(8)-H(8A) 109.5 C(3)-C(8)-H(8B) 109.5 H(8A)-C(8)-H(8B) 109.5 C(3)-C(8)-H(8C) 109.5 H(8A)-C(8)-H(8C) 109.5 H(8B)-C(8)-H(8C) 109.5 N(1)-C(9)-H(9A) 109.5 N(1)-C(9)-H(9B) 109.5 H(9A)-C(9)-H(9B) 109.5 N(1)-C(9)-H(9C) 109.5 H(9A)-C(9)-H(9C) 109.5 H(9B)-C(9)-H(9C) 109.5 C(11)-C(10)-C(15) 116.46(14) C(11)-C(10)-B(1) 122.24(14) C(15)-C(10)-B(1) 121.18(14) C(12)-C(11)-C(10) 122.39(14) C(12)-C(11)-H(11) 118.8 C(10)-C(11)-H(11) 118.8 C(13)-C(12)-C(11) 119.87(14) C(13)-C(12)-H(12) 120.1 C(11)-C(12)-H(12) 120.1 FH12768200.3 UIX-05025 C(12)-C(13)-C(14) 118.97(14) C(12)-C(13)-C(16) 122.95(14) C(14)-C(13)-C(16) 118.07(14) C(15)-C(14)-C(13) 120.57(15) C(15)-C(14)-H(14) 119.7 C(13)-C(14)-H(14) 119.7 C(14)-C(15)-C(10) 121.73(14) C(14)-C(15)-H(15) 119.1 C(10)-C(15)-H(15) 119.1 O(5)-C(16)-C(13) 112.11(13) O(5)-C(16)-H(16A) 109.2 C(13)-C(16)-H(16A) 109.2 O(5)-C(16)-H(16B) 109.2 C(13)-C(16)-H(16B) 109.2 H(16A)-C(16)-H(16B) 107.9 O(6)-C(17)-N(2) 127.30(16) O(6)-C(17)-O(5) 124.08(15) N(2)-C(17)-O(5) 108.62(14) C(19)-C(18)-C(23) 118.90(15) C(19)-C(18)-N(2) 124.97(15) C(23)-C(18)-N(2) 116.07(14) C(20)-C(19)-C(18) 119.57(15) C(20)-C(19)-H(19) 120.2 C(18)-C(19)-H(19) 120.2 C(19)-C(20)-C(21) 121.94(15) C(19)-C(20)-H(20) 119.0 C(21)-C(20)-H(20) 119.0 C(20)-C(21)-C(22) 117.62(15) C(20)-C(21)-C(24) 122.35(14) C(22)-C(21)-C(24) 120.02(14) C(23)-C(22)-C(21) 121.03(15) C(23)-C(22)-H(22) 119.5 C(21)-C(22)-H(22) 119.5 C(22)-C(23)-C(18) 120.92(15) C(22)-C(23)-H(23) 119.5 C(18)-C(23)-H(23) 119.5 FH12768200.3 UIX-05025 C(29)-C(24)-C(25) 118.01(15) C(29)-C(24)-C(21) 121.02(15) C(25)-C(24)-C(21) 120.96(14) C(26)-C(25)-C(24) 120.93(15) C(26)-C(25)-H(25) 119.5 C(24)-C(25)-H(25) 119.5 C(27)-C(26)-C(25) 120.27(16) C(27)-C(26)-H(26) 119.9 C(25)-C(26)-H(26) 119.9 C(26)-C(27)-C(28) 119.68(16) C(26)-C(27)-H(27) 120.2 C(28)-C(27)-H(27) 120.2 C(27)-C(28)-C(29) 120.14(16) C(27)-C(28)-H(28) 119.9 C(29)-C(28)-H(28) 119.9 C(28)-C(29)-C(24) 120.96(16) C(28)-C(29)-H(29) 119.5 C(24)-C(29)-H(29) 119.5 O(1)-B(1)-O(4) 113.97(13) O(1)-B(1)-C(10) 110.37(13) O(4)-B(1)-C(10) 111.75(13) O(1)-B(1)-N(1) 101.22(12) O(4)-B(1)-N(1) 99.34(11) C(10)-B(1)-N(1) 119.63(13) _____________________________________________________________ Symmetry transformations used to generate equivalent atoms:Table 17. Anisotropic displacement parameters (Å2x 103) for 10957d1s.The anisotropic displacement factor exponent takes the form: -2p2[ h2a*2U11+ ... + 2 h k a*b* U12]______________________________________________________________________________ U11U22U33U23U13U12______________________________________________________________________________ O(1) 15(1) 31(1) 25(1) 6(1) 3(1) -1(1) O(2) 21(1) 56(1) 23(1) 4(1) 0(1) 3(1) O(3) 31(1) 23(1) 25(1) -5(1) 5(1) 1(1) FH12768200.3 UIX-05025 O(4) 18(1) 16(1) 26(1) 0(1) 6(1) -1(1) O(5) 16(1) 24(1) 26(1) 1(1) -1(1) 0(1) O(6) 39(1) 20(1) 31(1) -3(1) -3(1) -2(1) N(1) 13(1) 20(1) 21(1) -2(1) 3(1) -1(1) N(2) 20(1) 18(1) 28(1) 2(1) 1(1) -1(1) C(1) 16(1) 32(1) 25(1) -1(1) 4(1) 2(1) C(2) 14(1) 32(1) 22(1) -1(1) 1(1) -2(1) C(3) 20(1) 20(1) 19(1) -1(1) 5(1) -1(1) C(4) 14(1) 21(1) 23(1) 1(1) 0(1) 1(1) C(5) 22(1) 41(1) 32(1) -4(1) 0(1) -11(1) C(6) 18(1) 38(1) 29(1) 2(1) 4(1) 5(1) C(7) 23(1) 23(1) 25(1) 4(1) 3(1) 0(1) C(8) 22(1) 24(1) 27(1) 1(1) 9(1) -2(1) C(9) 22(1) 21(1) 30(1) -4(1) 8(1) -3(1) C(10) 14(1) 18(1) 24(1) 2(1) 4(1) -2(1) C(11) 18(1) 19(1) 23(1) -2(1) 5(1) -2(1) C(12) 16(1) 23(1) 23(1) -2(1) 0(1) -2(1) C(13) 15(1) 19(1) 25(1) 3(1) 3(1) -2(1) C(14) 19(1) 26(1) 21(1) -1(1) 5(1) -1(1) C(15) 17(1) 28(1) 20(1) 0(1) 1(1) -3(1) C(16) 17(1) 31(1) 24(1) -3(1) 1(1) 1(1) C(17) 14(1) 23(1) 25(1) -1(1) 5(1) 2(1) C(18) 14(1) 23(1) 24(1) 0(1) 4(1) 2(1) C(19) 17(1) 19(1) 28(1) -4(1) 3(1) 0(1) C(20) 19(1) 17(1) 30(1) 1(1) 4(1) 1(1) C(21) 12(1) 22(1) 26(1) -1(1) 5(1) 2(1) C(22) 23(1) 20(1) 28(1) -2(1) 1(1) -4(1) C(23) 25(1) 19(1) 30(1) 1(1) 1(1) -3(1) C(24) 18(1) 21(1) 26(1) -1(1) 4(1) 3(1) C(25) 17(1) 23(1) 31(1) 1(1) 4(1) 1(1) C(26) 28(1) 33(1) 29(1) 6(1) 7(1) 1(1) C(27) 30(1) 42(1) 24(1) 3(1) -2(1) 2(1) C(28) 22(1) 43(1) 31(1) -2(1) -2(1) -5(1) C(29) 21(1) 32(1) 28(1) 0(1) 4(1) -4(1) B(1) 17(1) 18(1) 24(1) 2(1) 4(1) -2(1) ______________________________________________________________________________ FH12768200.3 UIX-05025Table 18. Hydrogen coordinates (x 104) and isotropic displacement parameters (Å2x103)for 10957d1s. ______________________________________________________________________________ x y z U(eq) ______________________________________________________________________________ H(2) 3909(11) 1410(20) 5343(7) 33 H(5A) 10340 3680 6428 48 H(5B) 10649 2885 6899 48 H(5C) 9945 3807 6922 48 H(6A) 9775 445 6186 43 H(6B) 10455 696 6598 43 H(6C) 10421 1431 6090 43 H(7A) 8234 3029 5073 35 H(7B) 8360 4144 5463 35 H(7C) 7819 2990 5561 35 H(8A) 9602 2973 5127 36 H(8B) 10095 2512 5612 36 H(8C) 9743 3899 5585 36 H(9A) 9030 4493 6302 36 H(9B) 8718 3833 6763 36 H(9C) 8177 4010 6269 36 H(11) 7098 1103 5671 24 H(12) 5819 1485 5693 25 H(14) 6252 2895 7056 26 H(15) 7526 2510 7031 26 H(16A) 4935 2134 6721 29 H(16B) 5007 3429 6433 29 H(19) 3896 4489 4878 26 H(20) 3324 5022 4108 26 H(22) 2513 1485 3923 29 H(23) 3086 939 4685 30 H(25) 3370 4732 3233 29 H(26) 2842 5166 2444 35 H(27) 1659 4370 2165 39 H(28) 1012 3106 2676 39 FH12768200.3 UIX-05025 H(29) 1552 2617 3458 33 Table 19. Torsion angles [°] for 10957d1s. ________________________________________________________________ B(1)-O(1)-C(1)-O(2) 171.59(16) B(1)-O(1)-C(1)-C(2) -12.81(19) O(2)-C(1)-C(2)-C(5) -32.6(2) O(1)-C(1)-C(2)-C(5) 151.81(15) O(2)-C(1)-C(2)-C(6) 84.7(2) O(1)-C(1)-C(2)-C(6) -90.88(15) O(2)-C(1)-C(2)-N(1) -154.85(17) O(1)-C(1)-C(2)-N(1) 29.58(17) C(9)-N(1)-C(2)-C(5) -35.03(17) C(3)-N(1)-C(2)-C(5) 94.98(16) B(1)-N(1)-C(2)-C(5) -153.79(13) C(9)-N(1)-C(2)-C(1) 86.70(14) C(3)-N(1)-C(2)-C(1) -143.28(13) B(1)-N(1)-C(2)-C(1) -32.05(14) C(9)-N(1)-C(2)-C(6) -163.01(13) C(3)-N(1)-C(2)-C(6) -33.00(19) B(1)-N(1)-C(2)-C(6) 78.23(15) C(9)-N(1)-C(3)-C(8) 83.63(16) C(2)-N(1)-C(3)-C(8) -44.61(18) B(1)-N(1)-C(3)-C(8) -154.99(13) C(9)-N(1)-C(3)-C(4) -151.95(12) C(2)-N(1)-C(3)-C(4) 79.81(14) B(1)-N(1)-C(3)-C(4) -30.57(14) C(9)-N(1)-C(3)-C(7) -39.36(16) C(2)-N(1)-C(3)-C(7) -167.60(13) B(1)-N(1)-C(3)-C(7) 82.02(14) B(1)-O(4)-C(4)-O(3) -178.09(15) B(1)-O(4)-C(4)-C(3) -0.96(17) N(1)-C(3)-C(4)-O(3) -161.27(14) C(8)-C(3)-C(4)-O(3) -35.3(2) C(7)-C(3)-C(4)-O(3) 82.96(18) FH12768200.3 UIX-05025 N(1)-C(3)-C(4)-O(4) 21.63(15) C(8)-C(3)-C(4)-O(4) 147.59(13) C(7)-C(3)-C(4)-O(4) -94.14(14) C(15)-C(10)-C(11)-C(12) 0.8(2) B(1)-C(10)-C(11)-C(12) 176.92(15) C(10)-C(11)-C(12)-C(13) -0.1(2) C(11)-C(12)-C(13)-C(14) -0.6(2) C(11)-C(12)-C(13)-C(16) -179.86(15) C(12)-C(13)-C(14)-C(15) 0.5(2) C(16)-C(13)-C(14)-C(15) 179.87(15) C(13)-C(14)-C(15)-C(10) 0.2(2) C(11)-C(10)-C(15)-C(14) -0.8(2) B(1)-C(10)-C(15)-C(14) -176.98(15) C(17)-O(5)-C(16)-C(13) -102.20(16) C(12)-C(13)-C(16)-O(5) 6.9(2) C(14)-C(13)-C(16)-O(5) -172.42(14) C(18)-N(2)-C(17)-O(6) 3.3(3) C(18)-N(2)-C(17)-O(5) -177.01(14) C(16)-O(5)-C(17)-O(6) -2.1(2) C(16)-O(5)-C(17)-N(2) 178.16(12) C(17)-N(2)-C(18)-C(19) 5.5(3) C(17)-N(2)-C(18)-C(23) -177.18(15) C(23)-C(18)-C(19)-C(20) -1.4(2) N(2)-C(18)-C(19)-C(20) 175.84(15) C(18)-C(19)-C(20)-C(21) 0.2(2) C(19)-C(20)-C(21)-C(22) 1.2(2) C(19)-C(20)-C(21)-C(24) -177.90(14) C(20)-C(21)-C(22)-C(23) -1.4(2) C(24)-C(21)-C(22)-C(23) 177.69(15) C(21)-C(22)-C(23)-C(18) 0.2(3) C(19)-C(18)-C(23)-C(22) 1.2(2) N(2)-C(18)-C(23)-C(22) -176.31(15) C(20)-C(21)-C(24)-C(29) -142.02(16) C(22)-C(21)-C(24)-C(29) 38.9(2) C(20)-C(21)-C(24)-C(25) 39.1(2) C(22)-C(21)-C(24)-C(25) -139.93(16) FH12768200.3 UIX-05025 C(29)-C(24)-C(25)-C(26) -0.6(2) C(21)-C(24)-C(25)-C(26) 178.34(15) C(24)-C(25)-C(26)-C(27) 1.1(3) C(25)-C(26)-C(27)-C(28) -0.5(3) C(26)-C(27)-C(28)-C(29) -0.5(3) C(27)-C(28)-C(29)-C(24) 1.0(3) C(25)-C(24)-C(29)-C(28) -0.5(3) C(21)-C(24)-C(29)-C(28) -179.36(16) C(1)-O(1)-B(1)-O(4) 96.64(16) C(1)-O(1)-B(1)-C(10) -136.66(14) C(1)-O(1)-B(1)-N(1) -8.98(17) C(4)-O(4)-B(1)-O(1) -125.04(14) C(4)-O(4)-B(1)-C(10) 108.98(14) C(4)-O(4)-B(1)-N(1) -18.25(15) C(11)-C(10)-B(1)-O(1) -140.37(15) C(15)-C(10)-B(1)-O(1) 35.6(2) C(11)-C(10)-B(1)-O(4) -12.4(2) C(15)-C(10)-B(1)-O(4) 163.49(14) C(11)-C(10)-B(1)-N(1) 102.89(18) C(15)-C(10)-B(1)-N(1) -81.18(19) C(9)-N(1)-B(1)-O(1) -90.83(14) C(3)-N(1)-B(1)-O(1) 147.11(12) C(2)-N(1)-B(1)-O(1) 25.98(14) C(9)-N(1)-B(1)-O(4) 152.28(12) C(3)-N(1)-B(1)-O(4) 30.21(13) C(2)-N(1)-B(1)-O(4) -90.91(12) C(9)-N(1)-B(1)-C(10) 30.57(19) C(3)-N(1)-B(1)-C(10) -91.49(15) C(2)-N(1)-B(1)-C(10) 147.38(14) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms FH12768200.3 UIX-05025 Table 20. Hydrogen bonds for 10957d1s [Å and °]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(2)-H(2)...O(3)#1 0.84(2) 2.14(2) 2.9581(19) 162.4(19) ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 x-1 / 2,-y,z Crystal data and structure refinement for 19 (10941ds), CCDC Number: 2291892 are provided below. Table 21. Crystal data and structure refinement for 10941ds. FH12768200.3 UIX-05025 Table 22. Atomic coordinates (x 104) and equivalent isotropic displacement parameters(Å2x103) for 10941ds. U(eq) is defined as one third of the trace of the orthogonalized Uijtensor. ______________________________________________________________________________ x y z U(eq) ______________________________________________________________________________ Br(1) -7470(1) 344(1) 3562(1) 18(1) O(1) 8842(2) 8321(1) 8846(1) 15(1) O(2) 10821(2) 9859(1) 8572(1) 21(1) O(3) 10355(2) 6351(1) 11225(1) 21(1) O(4) 8568(2) 6798(1) 9859(1) 16(1) O(5) 636(2) 3925(1) 6248(1) 23(1) O(6) -583(2) 2322(1) 5144(1) 25(1) N(1) 11246(2) 7220(1) 8864(1) 12(1) N(2) -2219(2) 2878(1) 6457(1) 20(1) N(3) -4719(2) 1701(1) 5178(1) 16(1) N(4) -4912(2) 1858(1) 6998(1) 18(1) C(1) 10518(2) 8902(1) 8613(1) 15(1) C(2) 11922(2) 8175(1) 8318(1) 14(1) FH12768200.3 UIX-05025 C(3) 12068(2) 7400(1) 10058(1) 14(1) C(4) 10273(2) 6766(1) 10447(1) 16(1) C(5) 11377(2) 7834(1) 7122(1) 17(1) C(6) 14155(2) 8719(1) 8565(1) 18(1) C(7) 13988(2) 7024(1) 10333(1) 19(1) C(8) 12298(3) 8562(1) 10658(1) 19(1) C(9) 11591(2) 6175(1) 8343(1) 16(1) C(10) 7190(2) 6352(1) 7944(1) 14(1) C(11) 6303(2) 6678(1) 7052(1) 15(1) C(12) 4762(2) 5967(1) 6320(1) 17(1) C(13) 4042(2) 4907(1) 6469(1) 18(1) C(14) 4900(3) 4570(1) 7354(1) 20(1) C(15) 6442(2) 5276(1) 8073(1) 18(1) C(16) 2349(3) 4131(2) 5711(1) 23(1) C(17) -714(2) 2976(1) 5864(1) 18(1) C(18) -4020(2) 2093(1) 6191(1) 16(1) C(19) -6388(2) 921(1) 4991(1) 16(1) C(20) -7397(2) 528(1) 5755(1) 19(1) C(21) -6609(2) 1070(1) 6762(1) 19(1) B(1) 8844(3) 7161(1) 8851(1) 14(1) Table 23. Bond lengths [Å] and angles [°] for 10941ds. _____________________________________________________ Br(1)-C(19) 1.9012(16) O(1)-C(1) 1.3369(19) O(1)-B(1) 1.485(2) O(2)-C(1) 1.206(2) O(3)-C(4) 1.211(2) O(4)-C(4) 1.3295(19) O(4)-B(1) 1.483(2) O(5)-C(17) 1.350(2) O(5)-C(16) 1.458(2) O(6)-C(17) 1.201(2) N(1)-C(9) 1.4986(19) N(1)-C(2) 1.5193(19) FH12768200.3 UIX-05025 N(1)-C(3) 1.5569(19) N(1)-B(1) 1.649(2) N(2)-C(17) 1.381(2) N(2)-C(18) 1.392(2) N(2)-H(2) 0.83(2) N(3)-C(19) 1.325(2) N(3)-C(18) 1.337(2) N(4)-C(18) 1.335(2) N(4)-C(21) 1.343(2) C(1)-C(2) 1.536(2) C(2)-C(6) 1.525(2) C(2)-C(5) 1.539(2) C(3)-C(7) 1.524(2) C(3)-C(4) 1.525(2) C(3)-C(8) 1.549(2) C(5)-H(5A) 0.9800 C(5)-H(5B) 0.9800 C(5)-H(5C) 0.9800 C(6)-H(6A) 0.9800 C(6)-H(6B) 0.9800 C(6)-H(6C) 0.9800 C(7)-H(7A) 0.9800 C(7)-H(7B) 0.9800 C(7)-H(7C) 0.9800 C(8)-H(8A) 0.9800 C(8)-H(8B) 0.9800 C(8)-H(8C) 0.9800 C(9)-H(9A) 0.9800 C(9)-H(9B) 0.9800 C(9)-H(9C) 0.9800 C(10)-C(11) 1.400(2) C(10)-C(15) 1.405(2) C(10)-B(1) 1.605(2) C(11)-C(12) 1.397(2) C(11)-H(11) 0.9500 C(12)-C(13) 1.390(2) FH12768200.3 UIX-05025 C(12)-H(12) 0.9500 C(13)-C(14) 1.392(2) C(13)-C(16) 1.503(2) C(14)-C(15) 1.387(2) C(14)-H(14) 0.9500 C(15)-H(15) 0.9500 C(16)-H(16A) 0.9900 C(16)-H(16B) 0.9900 C(19)-C(20) 1.389(2) C(20)-C(21) 1.381(2) C(20)-H(20) 0.9500 C(21)-H(21) 0.9500 C(1)-O(1)-B(1) 113.67(12) C(4)-O(4)-B(1) 113.47(12) C(17)-O(5)-C(16) 114.68(13) C(9)-N(1)-C(2) 113.47(12) C(9)-N(1)-C(3) 109.61(12) C(2)-N(1)-C(3) 115.70(12) C(9)-N(1)-B(1) 112.04(12) C(2)-N(1)-B(1) 103.59(11) C(3)-N(1)-B(1) 101.67(11) C(17)-N(2)-C(18) 124.39(15) C(17)-N(2)-H(2) 116.8(17) C(18)-N(2)-H(2) 117.5(17) C(19)-N(3)-C(18) 114.35(14) C(18)-N(4)-C(21) 115.52(14) O(2)-C(1)-O(1) 124.15(15) O(2)-C(1)-C(2) 124.53(15) O(1)-C(1)-C(2) 111.15(13) N(1)-C(2)-C(6) 116.02(13) N(1)-C(2)-C(1) 101.52(12) C(6)-C(2)-C(1) 115.68(13) N(1)-C(2)-C(5) 111.00(12) C(6)-C(2)-C(5) 106.66(13) C(1)-C(2)-C(5) 105.53(12) C(7)-C(3)-C(4) 113.87(13) FH12768200.3 UIX-05025 C(7)-C(3)-C(8) 109.83(13) C(4)-C(3)-C(8) 101.44(12) C(7)-C(3)-N(1) 114.28(13) C(4)-C(3)-N(1) 100.94(12) C(8)-C(3)-N(1) 115.56(12) O(3)-C(4)-O(4) 123.79(15) O(3)-C(4)-C(3) 125.42(15) O(4)-C(4)-C(3) 110.61(13) C(2)-C(5)-H(5A) 109.5 C(2)-C(5)-H(5B) 109.5 H(5A)-C(5)-H(5B) 109.5 C(2)-C(5)-H(5C) 109.5 H(5A)-C(5)-H(5C) 109.5 H(5B)-C(5)-H(5C) 109.5 C(2)-C(6)-H(6A) 109.5 C(2)-C(6)-H(6B) 109.5 H(6A)-C(6)-H(6B) 109.5 C(2)-C(6)-H(6C) 109.5 H(6A)-C(6)-H(6C) 109.5 H(6B)-C(6)-H(6C) 109.5 C(3)-C(7)-H(7A) 109.5 C(3)-C(7)-H(7B) 109.5 H(7A)-C(7)-H(7B) 109.5 C(3)-C(7)-H(7C) 109.5 H(7A)-C(7)-H(7C) 109.5 H(7B)-C(7)-H(7C) 109.5 C(3)-C(8)-H(8A) 109.5 C(3)-C(8)-H(8B) 109.5 H(8A)-C(8)-H(8B) 109.5 C(3)-C(8)-H(8C) 109.5 H(8A)-C(8)-H(8C) 109.5 H(8B)-C(8)-H(8C) 109.5 N(1)-C(9)-H(9A) 109.5 N(1)-C(9)-H(9B) 109.5 H(9A)-C(9)-H(9B) 109.5 N(1)-C(9)-H(9C) 109.5 FH12768200.3 UIX-05025 H(9A)-C(9)-H(9C) 109.5 H(9B)-C(9)-H(9C) 109.5 C(11)-C(10)-C(15) 116.76(14) C(11)-C(10)-B(1) 123.62(14) C(15)-C(10)-B(1) 119.41(14) C(12)-C(11)-C(10) 121.72(15) C(12)-C(11)-H(11) 119.1 C(10)-C(11)-H(11) 119.1 C(13)-C(12)-C(11) 120.40(15) C(13)-C(12)-H(12) 119.8 C(11)-C(12)-H(12) 119.8 C(12)-C(13)-C(14) 118.69(15) C(12)-C(13)-C(16) 121.70(16) C(14)-C(13)-C(16) 119.61(15) C(15)-C(14)-C(13) 120.69(15) C(15)-C(14)-H(14) 119.7 C(13)-C(14)-H(14) 119.7 C(14)-C(15)-C(10) 121.74(15) C(14)-C(15)-H(15) 119.1 C(10)-C(15)-H(15) 119.1 O(5)-C(16)-C(13) 107.17(13) O(5)-C(16)-H(16A) 110.3 C(13)-C(16)-H(16A) 110.3 O(5)-C(16)-H(16B) 110.3 C(13)-C(16)-H(16B) 110.3 H(16A)-C(16)-H(16B) 108.5 O(6)-C(17)-O(5) 125.13(15) O(6)-C(17)-N(2) 126.43(15) O(5)-C(17)-N(2) 108.42(14) N(4)-C(18)-N(3) 127.20(15) N(4)-C(18)-N(2) 114.73(15) N(3)-C(18)-N(2) 117.97(14) N(3)-C(19)-C(20) 124.79(15) N(3)-C(19)-Br(1) 116.26(12) C(20)-C(19)-Br(1) 118.93(12) C(21)-C(20)-C(19) 114.71(15) FH12768200.3 UIX-05025 C(21)-C(20)-H(20) 122.6 C(19)-C(20)-H(20) 122.6 N(4)-C(21)-C(20) 122.94(15) N(4)-C(21)-H(21) 118.5 C(20)-C(21)-H(21) 118.5 O(4)-B(1)-O(1) 114.19(13) O(4)-B(1)-C(10) 108.05(13) O(1)-B(1)-C(10) 112.85(13) O(4)-B(1)-N(1) 101.38(12) O(1)-B(1)-N(1) 99.88(11) C(10)-B(1)-N(1) 120.12(13) _____________________________________________________________ Symmetry transformations used to generate equivalent atomsTable 24. Anisotropic displacement parameters (Å2x 103) for 10941ds.The anisotropic displacement factor exponent takes the form: -2p2[ h2a*2U11+ ... + 2 h k a*b* U12]______________________________________________________________________________ U11U22U33U23U13U12______________________________________________________________________________ Br(1) 16(1) 20(1) 18(1) 4(1) 1(1) 2(1) O(1) 12(1) 14(1) 19(1) 2(1) 4(1) 4(1) O(2) 25(1) 14(1) 24(1) 4(1) 6(1) 6(1) O(3) 21(1) 22(1) 18(1) 7(1) 4(1) 3(1) O(4) 12(1) 22(1) 16(1) 5(1) 5(1) 4(1) O(5) 17(1) 21(1) 25(1) -6(1) 9(1) -5(1) O(6) 21(1) 27(1) 22(1) -5(1) 6(1) -2(1) N(1) 11(1) 12(1) 14(1) 2(1) 4(1) 3(1) N(2) 17(1) 22(1) 17(1) -3(1) 5(1) -3(1) N(3) 15(1) 16(1) 18(1) 3(1) 4(1) 3(1) N(4) 17(1) 18(1) 19(1) 4(1) 5(1) 2(1) C(1) 15(1) 16(1) 14(1) 2(1) 1(1) 3(1) C(2) 13(1) 12(1) 17(1) 4(1) 4(1) 2(1) C(3) 13(1) 17(1) 13(1) 3(1) 3(1) 3(1) C(4) 15(1) 15(1) 16(1) 2(1) 4(1) 3(1) C(5) 16(1) 19(1) 16(1) 4(1) 5(1) 4(1) FH12768200.3 UIX-05025 C(6) 14(1) 18(1) 22(1) 4(1) 5(1) 0(1) C(7) 15(1) 23(1) 21(1) 6(1) 2(1) 7(1) C(8) 20(1) 18(1) 17(1) 0(1) 3(1) 3(1) C(9) 16(1) 12(1) 20(1) 1(1) 5(1) 4(1) C(10) 10(1) 15(1) 19(1) 2(1) 5(1) 3(1) C(11) 13(1) 15(1) 18(1) 3(1) 6(1) 2(1) C(12) 13(1) 22(1) 16(1) 2(1) 5(1) 3(1) C(13) 13(1) 18(1) 20(1) -3(1) 6(1) 0(1) C(14) 17(1) 13(1) 28(1) 2(1) 6(1) 2(1) C(15) 15(1) 16(1) 24(1) 6(1) 3(1) 4(1) C(16) 16(1) 26(1) 22(1) -4(1) 8(1) -4(1) C(17) 15(1) 19(1) 16(1) 1(1) 1(1) -1(1) C(18) 14(1) 14(1) 21(1) 2(1) 4(1) 2(1) C(19) 14(1) 17(1) 16(1) 3(1) 0(1) 4(1) C(20) 14(1) 20(1) 23(1) 7(1) 2(1) 1(1) C(21) 16(1) 22(1) 21(1) 8(1) 6(1) 3(1) B(1) 11(1) 15(1) 16(1) 3(1) 4(1) 3(1) ______________________________________________________________________________Table 25. Hydrogen coordinates (x 104) and isotropic displacement parameters (Å2x 103)for 10941ds. ______________________________________________________________________________ x y z U(eq) ______________________________________________________________________________ H(2) -1930(40) 3220(20) 7065(19) 30 H(5A) 11543 8484 6792 25 H(5B) 9981 7416 6931 25 H(5C) 12260 7386 6880 25 H(6A) 14921 8189 8358 27 H(6B) 14550 8994 9317 27 H(6C) 14428 9324 8179 27 H(7A) 13771 6255 10033 29 H(7B) 14362 7120 11095 29 H(7C) 15067 7456 10049 29 H(8A) 13352 9069 10427 28 FH12768200.3 UIX-05025 H(8B) 12659 8571 11410 28 H(8C) 11027 8779 10518 28 H(9A) 10788 5970 7639 24 H(9B) 11197 5603 8753 24 H(9C) 13015 6269 8297 24 H(11) 6762 7402 6941 18 H(12) 4202 6209 5717 20 H(14) 4423 3848 7467 23 H(15) 7008 5025 8669 22 H(16A) 2011 4452 5083 27 H(16B) 2733 3444 5489 27 H(20) -8539 -66 5598 23 H(21) -7299 877 7311 23 Table 26. Torsion angles [°] for 10941ds. ________________________________________________________________ B(1)-O(1)-C(1)-O(2) -179.65(15) B(1)-O(1)-C(1)-C(2) 4.98(18) C(9)-N(1)-C(2)-C(6) -81.29(16) C(3)-N(1)-C(2)-C(6) 46.67(18) B(1)-N(1)-C(2)-C(6) 156.99(13) C(9)-N(1)-C(2)-C(1) 152.44(12) C(3)-N(1)-C(2)-C(1) -79.61(14) B(1)-N(1)-C(2)-C(1) 30.72(14) C(9)-N(1)-C(2)-C(5) 40.67(17) C(3)-N(1)-C(2)-C(5) 168.62(12) B(1)-N(1)-C(2)-C(5) -81.05(14) O(2)-C(1)-C(2)-N(1) 160.80(15) O(1)-C(1)-C(2)-N(1) -23.86(16) O(2)-C(1)-C(2)-C(6) 34.3(2) O(1)-C(1)-C(2)-C(6) -150.36(13) O(2)-C(1)-C(2)-C(5) -83.34(19) O(1)-C(1)-C(2)-C(5) 92.01(15) C(9)-N(1)-C(3)-C(7) 36.72(17) C(2)-N(1)-C(3)-C(7) -93.13(15) FH12768200.3 UIX-05025 B(1)-N(1)-C(3)-C(7) 155.42(13) C(9)-N(1)-C(3)-C(4) -85.93(13) C(2)-N(1)-C(3)-C(4) 144.23(12) B(1)-N(1)-C(3)-C(4) 32.78(13) C(9)-N(1)-C(3)-C(8) 165.63(13) C(2)-N(1)-C(3)-C(8) 35.79(17) B(1)-N(1)-C(3)-C(8) -75.66(15) B(1)-O(4)-C(4)-O(3) -169.24(15) B(1)-O(4)-C(4)-C(3) 15.52(18) C(7)-C(3)-C(4)-O(3) 30.3(2) C(8)-C(3)-C(4)-O(3) -87.61(19) N(1)-C(3)-C(4)-O(3) 153.22(16) C(7)-C(3)-C(4)-O(4) -154.55(14) C(8)-C(3)-C(4)-O(4) 87.54(15) N(1)-C(3)-C(4)-O(4) -31.63(16) C(15)-C(10)-C(11)-C(12) -0.5(2) B(1)-C(10)-C(11)-C(12) -175.13(14) C(10)-C(11)-C(12)-C(13) 0.9(2) C(11)-C(12)-C(13)-C(14) -0.6(2) C(11)-C(12)-C(13)-C(16) 178.35(15) C(12)-C(13)-C(14)-C(15) -0.1(2) C(16)-C(13)-C(14)-C(15) -178.99(15) C(13)-C(14)-C(15)-C(10) 0.4(3) C(11)-C(10)-C(15)-C(14) -0.1(2) B(1)-C(10)-C(15)-C(14) 174.75(15) C(17)-O(5)-C(16)-C(13) -155.89(15) C(12)-C(13)-C(16)-O(5) -111.96(17) C(14)-C(13)-C(16)-O(5) 66.9(2) C(16)-O(5)-C(17)-O(6) 0.3(3) C(16)-O(5)-C(17)-N(2) 178.73(14) C(18)-N(2)-C(17)-O(6) -12.4(3) C(18)-N(2)-C(17)-O(5) 169.22(16) C(21)-N(4)-C(18)-N(3) 6.4(2) C(21)-N(4)-C(18)-N(2) -177.39(15) C(19)-N(3)-C(18)-N(4) -6.9(2) C(19)-N(3)-C(18)-N(2) 176.97(15) FH12768200.3 UIX-05025 C(17)-N(2)-C(18)-N(4) 155.51(16) C(17)-N(2)-C(18)-N(3) -27.9(2) C(18)-N(3)-C(19)-C(20) 1.0(2) C(18)-N(3)-C(19)-Br(1) 179.29(11) N(3)-C(19)-C(20)-C(21) 4.5(3) Br(1)-C(19)-C(20)-C(21) -173.81(12) C(18)-N(4)-C(21)-C(20) 0.2(2) C(19)-C(20)-C(21)-N(4) -5.0(3) C(4)-O(4)-B(1)-O(1) -99.51(15) C(4)-O(4)-B(1)-C(10) 134.04(13) C(4)-O(4)-B(1)-N(1) 6.88(16) C(1)-O(1)-B(1)-O(4) 121.87(14) C(1)-O(1)-B(1)-C(10) -114.22(14) C(1)-O(1)-B(1)-N(1) 14.55(16) C(11)-C(10)-B(1)-O(4) 146.82(14) C(15)-C(10)-B(1)-O(4) -27.64(19) C(11)-C(10)-B(1)-O(1) 19.6(2) C(15)-C(10)-B(1)-O(1) -154.86(14) C(11)-C(10)-B(1)-N(1) -97.78(18) C(15)-C(10)-B(1)-N(1) 87.77(18) C(9)-N(1)-B(1)-O(4) 91.72(14) C(2)-N(1)-B(1)-O(4) -145.61(12) C(3)-N(1)-B(1)-O(4) -25.24(14) C(9)-N(1)-B(1)-O(1) -150.94(12) C(2)-N(1)-B(1)-O(1) -28.27(14) C(3)-N(1)-B(1)-O(1) 92.10(12) C(9)-N(1)-B(1)-C(10) -27.11(18) C(2)-N(1)-B(1)-C(10) 95.56(15) C(3)-N(1)-B(1)-C(10) -144.07(14) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms: FH12768200.3 UIX-05025 Table 27. Hydrogen bonds for 10941ds [Å and °]. ____________________________________________________________________________ D-H...A d(D-H) d(H...A) d(D...A) <(DHA) ____________________________________________________________________________ N(2)-H(2)...O(3)#1 0.83(2) 2.29(2) 3.0700(19) 156(2) ____________________________________________________________________________ Symmetry transformations used to generate equivalent atoms: #1 -x+1,-y+1,-z+2 INCORPORATION BY REFERENCE All US patents and US and PCT patent application publications mentioned herein are hereby incorporated by reference in their entirety as if each individual publication or patent was specifically and individually indicated to be incorporated by reference. In case of conflict, the present application, including any definitions herein, will control. EQUIVALENTS While specific embodiments of the subject invention have been discussed, the above specification is illustrative and not restrictive. Many variations of the invention will become apparent to those skilled in the art upon review of this specification and the claims below. The full scope of the invention should be determined by reference to the claims, along with their full scope of equivalents, and the specification, along with such variations. FH12768200.3

Claims

UIX-05025 CLAIMS We claim:

1. A method of making a compound of formula (I):comprising combining a compound of formula (II):and a compound of formula (III):thereby forming the compound of Formula I; wherein: A is aryl or heteroaryl; E is aryl or heteroaryl; B is a boron having sp3hybridization; n is an integer selected from 1, 2, 3, or 4; m is an integer selected from 0, 1, 2, 3, or 4; X1is halogen or -ORj; X2is halogen; Rjis selected from the group consisting of alkyl, nitrophenyl, pentafluorophenyl, and -N(C(O)CH2)2; R20is selected from the group consisting of H, alkyl, cycloalkyl, alkenyl, alkynyl, and aryl; 145 FH12768200.3UIX-05025 R21is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R22is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R23is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R24is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R25is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, halogen, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl; and R26is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl.

2. The method of claim 1, further comprising a base selected from the group consisting of triethylamine, pyridine, 2,6-lutidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 2,2,6,6- tetramethylpiperidine, NaHCO3, K2CO3, CsCO3, and K3PO4.

3. The method of claim 1 or 2, wherein A is phenyl.

4. The method of any one of claims 1-3, wherein each of R20, R21, R22, R23, and R24is methyl; or each of R21, R22, R23, and R24is methyl.

5. The method of any one of claims 1-4, wherein R25is H.

6. The method of any one of claims 1-5, wherein X1is chloro or fluoro.

7. The method of claim 6, wherein X1is chloro.

8. The method of any one of claims 1-5, wherein X1is ORj.

9. The method of claim 8, wherein Rjis selected from the group consisting of methyl, ethyl, nitrophenyl, pentafluorophenyl, and -N(C(O)CH2)2. 146 FH12768200.3UIX-05025 10. The method of any one of claims 1-9, wherein X2is bromo or iodo.

11. The method of any one of claims 1-10, wherein the method further comprises combining the compound of Formula (I), a compound of Formula (V):a palladium catalyst, and a base; thereby forming a compound of Formula (IV):wherein: G is aryl or heteroaryl; p is an integer selected from 0, 1, 2, 3, and 4; R27is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, halogen, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl; Y1is selected from the group consisting of -NH2, -B(pin), -B(neop), -B(dan), - B(MIDA), and -B(OH)2; and Y2is -NH- or is a bond.

12. The method of claim 11, wherein Y1is -NH2.

13. The method of claim 11, wherein Y1is -B(OH)2.

14. The method of claim 12, wherein Y2is -NH-.

15. The method of claim 13, wherein Y2is a bond. 147 FH12768200.3UIX-05025 16. The method of any one of claims 11-15, wherein the palladium catalyst is selected from the group consisting of (t-Bu-XPhos)Pd G3, (t-Bu-XPhos)Pd G4, (XPhos)Pd G3, (XPhos)Pd G4, Pd(PPh3)4, (RuPhos)Pd G3, (RuPhos)Pd G4, (XantPhos)Pd G3, (XantPhos)Pd G4, (t-Bu-P)3Pd G3, (t-Bu-P)3Pd G4, (SPhos)Pd G3, (Sphos)Pd G4, Pd(Oac)2, (Pd)2(DBA)3, and Pd(PPh3)2(Cl)2.

17. The method of claim 16, wherein the palladium catalyst is (t-Bu-XPhos)Pd G3 or (t- Bu-P)3Pd G4.

18. The method of any one of claims 11-17, wherein the base is selected from the group consisting of potassium trimethylsilanolate, triethylamine, pyridine, 2,6-lutidine, 1,8- diazabicyclo[5.4.0]undec-7-ene, 2,2,6,6-tetramethylpiperidine, NaHCO3, K2CO3, CsCO3, and K3PO4.

19. The method of claim 18, wherein the base is potassium trimethylsilanolate.

20. The method of any one of claims 11-19, wherein the method further comprises combining the compound of Formula (IV) and a reducing agent, thereby forming a compound of Formula (VI):(VI).

21. The method of claim 20, wherein the reducing agent is selected from the group consisting of BF3•Oet2, EtSH, TBAF, TMSI, Pd / C, H2, and NaBH4, or a combination of any of them.

22. The method of claim 21, wherein the reducing agent is the combination of Pd / C, NaBH4and H2. 148 FH12768200.3UIX-05025 23. The method of any one of claims 20-22, further comprising combining the compound of Formula (VI), a compound of Formula (VIII):an activating agent, and a base; thereby forming a compound of Formula (VII):(VII); wherein: J is aryl or heteroaryl; q is an integer selected from 0, 1, 2, 3, or 4; R28is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, halogen, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl; Y3is -C(O)2H or a carboxylate salt, and Y4is –C(O)-; or Y3is halogen, and Y4is a bond; when Y3is -CO2H or a carboxylate salt, the activating agent is selected from the group consisting of propylphosphonic anhydride, 1-ethyl-3-(3- dimethylaminopropyl)carbodiimide, benzotriazole-1-yl-oxy-tris-(dimethylamino)- phosphonium hexafluorophosphate, 1-[(1-(cyano-2-ethoxy-2-oxoethylideneaminooxy) dimethylaminomorpholino)] uronium hexafluorophosphate, hexafluorophosphate azabenzotriazole tetramethyluronium, hexafluorophosphate benzotriazole tetramethyluronium, benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate, and benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate; and 149 FH12768200.3UIX-05025 when Y3is halogen, the activating agent is selected from the group consisting of Pd(OAc)2, (SPhos)Pd(OAc)2, (SPhos)Pd G3, and (SPhos)Pd G4.

24. The method of claim 23, wherein Y3is CO2H or a carboxylate salt, and the activating agent is propylphosphonic anhydride; or wherein Y3is halogen, and the activating agent is (SPhos)Pd(OAc)2.

25. The method of claim 23 or 24, wherein the base is pyridine or Cs2CO3.

26. The method of any one of claims 23-25, wherein the method further comprises combining the compound of Formula (VII) and an oxidizing agent, thereby forming a compound of Formula (IX):(IX).

27. The method of claim 26, wherein the oxidizing agent is the combination of LiOH and H2O2.

28. The method of claim 26 or 27, wherein the method further comprises combining the compound of Formula (IX), a compound of Formula (XI):(XI), and a base; thereby forming a compound of Formula (X):wherein: 150 FH12768200.3UIX-05025 L is aryl or heteroaryl; X3is halogen; s is an integer selected from 0, 1, 2, 3, 4, or 5; and R29is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, heterocyclyl, heterocyclylalkyl, aryl, and heteroaryl.

29. The method of claim 28, wherein the base is pyridine.

30. The method of claim 28 or 29, wherein X3is chloro.

31. The method of any one of claims 28-30, wherein L is phenyl.

32. The method of any one of claims 28-31, wherein R29is N- methylpiperazinylmethylene.

33. The method of any one of claims 28-32, wherein s is 1.

34. The method of any one of claims 20-22, further comprising combining the compound of Formula (VI), a compound of Formula (XII):(XII); and a base; thereby forming a compound of Formula (XIII):(XIII); wherein: L is aryl or heteroaryl; X4is halogen; u is an integer selected from 0, 1, 2, 3, 4, or 5; and 151 FH12768200.3UIX-05025 R30is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, heterocyclyl, heterocyclylalkyl, aryl, and heteroaryl.

35. The method of claim 34, wherein L is aryl.

36. The method of claim 35, wherein L is phenyl.

37. The method of any one of claims 34-36, wherein X4is chloro.

38. The method of any one of claims 34-37, wherein the base is pyridine.

39. The method of any one of claims 20-22, further comprising combining the compound of Formula (VI), a compound of Formula (XIV): (XIV); and a base; thereby forming a compound of Formula (XV):wherein: X5is halogen; R31is selected from the group consisting of H, alkyl, cycloalkyl, heterocyclyl, and heterocyclylalkyl.

40. The method of claim 39, wherein X5is chloro.

41. The method of claim 39 or 40, wherein R31is alkyl.

42. The method of claim 41, wherein R31is butyl. 152 FH12768200.3UIX-05025 43. The method of any one of claims 40-42, wherein the base is pyridine.

44. A compound of Formula (I):or a salt thereof; wherein: A is aryl or heteroaryl; B is a boron having sp3hybridization; n is an integer selected from 1, 2, 3, or 4; X1is halogen or ORj; Rjis selected from the group consisting of alkyl, nitrophenyl, pentafluorophenyl, and -N(C(O)CH2)2; R20is selected from the group consisting of H, alkyl, cycloalkyl, alkenyl, alkynyl, and aryl; R21is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, and heteroaryl; R22is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, and heteroaryl; R23is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, and heteroaryl; R24is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, and heteroaryl; and R25is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, halogen, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl.

45. The compound of claim 44, wherein A is phenyl.

46. The compound of claim 44 or 45, wherein R25is H. 153 FH12768200.3UIX-05025 47. The compound of any one of claims 44-46, wherein at least one of R21, R22, R23, or R24is not H.

48. The compound of claim 47, wherein at least two of R21, R22, R23, or R24are not H.

49. The compound of claim 48, wherein at least three of R21, R22, R23, or R24are not H.

50. The compound of claim 49, wherein none of R21, R22, R23, or R24is H.

51. The compound of any one of claims 44-50, wherein each of R20, R21, R22, R23, and R24is methyl; or each of R21, R22, R23, and R24is methyl.

52. The compound of any one of claims 44-51, wherein X1is chloro or fluoro.

53. The compound of claim 52, wherein X1is chloro.

54. The compound of any one of claims 44-51, wherein X1is ORj.

55. The compound of claim 54, wherein Rjis selected from the group consisting of methyl, ethyl, nitrophenyl, pentafluorophenyl, and -N(C(O)CH2)2.

56. The compound of claim 55, wherein Rjis nitrophenyl.

57. The compound of claim 44, wherein the compound is:. The compound of claim 44, wherein the compound is: 154 FH12768200.3UIX-05025.

59. A method of making a compound of Formula (I), wherein the method comprises combining a compound of Formula (XVI):(XVI); and a compound of Formula (XVII):(XVII); thereby forming a compound of Formula (XVIII):(XVIII); and further combining the compound of Formula (XVIII) and a compound of Formula (XIX):(XIX); thereby forming the compound of Formula (I); wherein: A is aryl or heteroaryl; B is a boron having sp3hybridization; n is an integer selected from 1, 2, 3, or 4; X1is halogen or ORj; Rjis nitrophenyl; 155 FH12768200.3UIX-05025 R20is selected from the group consisting of H, alkyl, cycloalkyl, alkenyl, alkynyl, and aryl; R21is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R22is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R23is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R24is selected from the group consisting of H, alkyl, alkenyl, alkynyl, aryl, heteroaryl, aralkyl, and heteroaralkyl; R25is, independently for each occurrence, selected from the group consisting of H, alkyl, cycloalkyl, alkoxy, hydroxyl, halogen, acyl, aryl, heteroaryl, heterocyclyl, cyano, nitro, and sulfonyl; R30is haloalkyl or nitrophenyl; and R31is -(O)-haloalkyl or halogen.

60. The method of claim 59, wherein A is phenyl.

61. The method of claim 59 or 60, wherein R25is H.

62. The method of any one of claims 59-61, wherein X1is chloro or fluoro.

63. The method of any one of claims 59-61, wherein X1is ORj.

64. The method of claim 63, wherein Rjis 4-nitrophenyl.

65. The method of any one of claims 59-64, wherein each of R20, R21, R22, R23, and R24is methyl; or each of R21, R22, R23, and R24is methyl.

66. The method of any one of claims 59-65, wherein R30is -C(Cl)3.

67. The method of claim 66, wherein R31is -O(C(Cl)3).

68. The method of any one of claims 59-67, wherein R30is 4-nitrophenyl. 156 FH12768200.3UIX-05025 69. The method of claim 68, wherein R31is chloro.

70. The method of claim 59, wherein the compound of Formula (XVI) is:salt thereof.

71. The method of claim 59, wherein the compound of Formula (XVII) is:salt thereof.

72. The method of claim 59, wherein the compound of Formula (XVIII) is:salt thereof.

73. The method of claim 59, wherein the compound of Formula (XIX) is selected from the group consisting of:salt thereof.157 FH12768200.3

Images