A preparation method of geminal bis(boryl)cyclopropane compound

Abstract

The present invention belongs to the technical field of organic synthesis, and relates to a method for preparing a geminal bis(boryl)cyclopropane compound. The present invention forms a γ-iodine-substituted geminal di(boryl) ester compound intermediate by an intermolecular halogen atom transfer radical addition reaction, and then the γ-iodine-substituted geminal di(boryl) ester compound intermediate is deprotonated and alkylated in the presence of a base to produce a cyclization product, a geminal bis(boryl)cyclopropane compound. The method provided by the present invention can synthesize a geminal bis(boryl)cyclopropane compound by a one-pot method from an olefin combined with (diborylmethyl) iodide under visible light irradiation, is simple to operate, and provides a rapid way to synthesize highly functionalized compound molecules.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis and relates to a method for preparing a geminal bis(boryl)cyclopropane compound. Background Art

[0002] Cyclopropanes are a class of valuable compounds with properties such as high ring strain. They are widely present in bioactive molecules and drugs and are important building blocks in organic synthesis. Many methods have been developed to obtain these small carbon rings, such as [2+1] cyclopropanation methods, such as Simmons-Smith reaction (Simmons, HE; ​​Smith, RD; A New Synthesis of Cyclopropanes from Olefins[J]), carbene-like migration insertion (Qin, C.; Boyarskikh, V.; Hansen, JH; et al. D2-Symmetric Dirhodium Catalyst Derivedfrom a 1,2,2-Triarylcyclopropanecarboxylate Ligand: Design, Synthesis and Application[J]) and ylide-type cyclopropanation (Johnson, JD; Teeples, CR; Akkawi, NR; et al. Efficient Synthesis of Orphaned Cyclopropanes Using Sulfones asCarbene Equivalents[J]). Although the above methods are feasible, the required starting materials are limited, which restricts the acquisition of certain types of cyclopropane compounds or introduces potential safety issues, thereby limiting the wide application of cyclopropane compounds.

[0003] Driven by a renewed interest in photochemistry, recent advances in chemical synthesis have established odd-electron intermediates as key drivers for building C-C bonds. These breakthroughs naturally extend to the synthesis of cyclopropanes, providing a practical and innovative platform for assembling three-membered carbon rings. Photoinduced radical cyclopropanation provides a practical alternative to traditional methods involving diazo reagents and metal carbenes. In 2016, photocatalytic cyclopropanation of olefins was achieved using diiodomethane as a methylene source (del Hoyo, AM; Herraiz, AG; Suero, MG; A Stereoconvergent Cyclopropanation Reaction of Styrenes[J]). The process uses visible light to activate the photocatalyst, which accepts electrons from diiodomethane in its excited state, resulting in homolytic cleavage of the C-I bond and formation of an iodomethyl radical, which then undergoes a "Giese" addition with the olefin to produce a reactive intermediate; subsequent C-C bond rotation positions the reactive intermediate for intramolecular SH2-type substitution, ultimately forming the cyclopropane. In 2018, a UVA-mediated borocyclopropanation of styrenes and diiodoborate was disclosed (Sayes, M.; Benoit, G.; Charette, AB; Borocyclopropanation of Styrenes Mediated by UV-light Under Continuous Flow Conditions[J]). In addition, radical polar crossover (RPC) also provides an ideal method to promote the synthesis of various functionalized cyclopropane compounds (Pitzer, L.; Schwarz, JL; Glorius, F.; Reductive Radical-Polar Crossover: Traditional Electrophiles in Modern Radical Reactions[J]). Under visible light, the photocatalyst undergoes single electron transfer (SET) with the carbene precursor to generate a radical carbene, which is added to the olefin to form a radical adduct. Subsequently, the reduced state of the photocatalyst promotes the SET reduction of the radical adduct intermediate to produce a carbanion complex, which undergoes an intramolecular cyclization reaction to generate cyclopropane compounds.

[0004] These aforementioned methods have obvious disadvantages, such as harsh conditions, tedious steps, challenging precursor synthesis, limited substrate scope and uncontrollable reactivity, which seriously hinder the discovery of multifunctional cyclopropane drugs. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a preparation method of a geminal bis(boryl)cyclopropane compound in view of the deficiencies in the prior art. The method is simple and efficient to operate and can synthesize the geminal bis(boryl)cyclopropane compound by combining a non-activated olefin with a (diborylmethyl)iodide.

[0006] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0007] The invention discloses a method for preparing a geminal bis(boryl)cyclopropane compound, wherein an olefin compound 1 and a (diborylmethyl)iodide 2 undergo a halogen atom transfer free radical addition reaction under the action of a catalyst and visible light, and then continue to undergo a deprotonation intramolecular cyclization reaction under the action of a base, thereby obtaining a geminal bis(boryl)cyclopropane compound 3;

[0008] The structural formula of the olefin compound 1 is shown in Formula 1, the structural formula of the (diborylmethyl)iodide 2 is shown in Formula 2, and the structural formula of the geminal bis(boryl)cyclopropane-containing compound 3 is shown in Formula 3:

[0009] ;

[0010] in,

[0011] R is selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C3-C6 cycloalkenyl, or substituted or unsubstituted aromatic group; wherein the substitution is selected from substitution by any number of identical or different substituents; the substituent is halogen, C1-C4 alkoxycarbonyl or C1-C4 alkoxy;

[0012] or,

[0013] R is selected from , or ;

[0014] n is an integer selected from 1 to 3;

[0015] R 1 is selected from substituted or unsubstituted aromatic groups;

[0016] m is an integer selected from 1 to 4;

[0017] R 2 is selected from substituted or unsubstituted aromatic groups, substituted or unsubstituted C3-C6 cycloalkyl groups, , , , or ;

[0018] z is an integer selected from 1 to 3;

[0019] R 3 , R 4 , R 5 Independently selected from substituted or unsubstituted C1-C4 alkyl, or substituted or unsubstituted aromatic group;

[0020] Wherein, the substitution is selected from substitution by any number of identical or different substituents; the substituent is halogen, C1-C4 alkyl substituted with 1 to 3 halogens, or C1-C4 alkyl.

[0021] In some embodiments, preferably, R is selected from substituted or unsubstituted C2-C5 alkyl, substituted or unsubstituted C6 cycloalkyl, substituted or unsubstituted C6 cycloalkenyl, or substituted or unsubstituted benzyl; wherein the substitution is selected from substitution by any number of identical or different substituents; the substituent is halogen, C1-C2 alkoxycarbonyl or C1-C2 alkoxy;

[0022] or,

[0023] R is selected from , or ;

[0024] n is an integer selected from 1 to 3;

[0025] R 1 is selected from substituted or unsubstituted naphthyl, substituted or unsubstituted phenyl, substituted or unsubstituted indolyl, substituted or unsubstituted azafluorenyl;

[0026] m is an integer selected from 1 to 4;

[0027] R 2 is selected from substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted C6 cycloalkyl, , , , or ;

[0028] z is an integer selected from 1 to 2;

[0029] R 3 , R 4 , R 5 Independently selected from C1-C2 alkyl or phenyl;

[0030] Wherein, the substitution is selected from substitution by any number of identical or different substituents; the substituent is halogen, C1-C2 alkyl or C1-C3 alkyl substituted with 1 to 3 halogens.

[0031] In some embodiments, further preferably, R is selected from substituted or unsubstituted ethyl, substituted or unsubstituted propyl, isobutyl, tert-butyl, pentyl, cyclohexyl, cyclohexenyl, or substituted or unsubstituted benzyl; wherein the substitution is selected from substitution by any number of identical or different substituents; the substituent is chlorine, methoxycarbonyl or methoxy;

[0032] or,

[0033] R is selected from , or ;

[0034] n is an integer selected from 1 to 3;

[0035] R 1 is selected from naphthyl, phenyl, substituted or unsubstituted indolyl, azafluorenyl;

[0036] m is an integer selected from 1 to 4;

[0037] R 2 is selected from substituted or unsubstituted phenyl, benzyl, substituted cyclohexyl, , , , or ;

[0038] z is selected from 2;

[0039] R 3 , R 4 , R 5 independently selected from methyl or phenyl;

[0040] Wherein, the substitution is selected from substitution by any number of identical or different substituents; the substituent is fluorine, chlorine, bromine, iodine, trifluoromethyl, methyl or isopropyl.

[0041] In some embodiments, the catalyst is dimanganese decacarbonyl or manganese pentacarbonyl bromide; the base is lithium diisopropylamide, lithium tetramethylpiperidinium or n-butyllithium.

[0042] In some embodiments, preferably, the catalyst is dimanganese decacarbonyl; and the base is lithium diisopropylamide or lithium tetramethylpiperidinium.

[0043] In some embodiments, the molar ratio of the olefin compound 1 to the (diboronmethyl) iodide 2 is (1.0-1.5):1.2; the molar ratio of the olefin compound 1 to the catalyst is 1.0:0.02-0.15.

[0044] In some embodiments, preferably, the molar ratio of the olefin compound 1 and the (diboronmethyl) iodide 2 is (1.0-1.2):1.2, and more preferably 1.0:1.2; the molar ratio of the olefin compound 1 and the catalyst is 1.0:(0.05-0.10), and more preferably 1.0:0.10.

[0045] In some embodiments, the visible light has a wavelength of 400-480 nm, preferably 440 nm.

[0046] In some embodiments, the reaction temperature of the halogen atom transfer radical addition reaction is 25° C. to 40° C.; the halogen atom transfer radical addition reaction is carried out under the protection of an inert gas.

[0047] Wherein, the inert gas is preferably nitrogen.

[0048] Wherein, the reaction time of the halogen atom transfer radical addition reaction is 30 min to 4 h, preferably 3 h.

[0049] In some embodiments, the solvent used in the halogen atom transfer radical addition reaction is n-hexane, dichloromethane or tetrahydrofuran.

[0050] In some embodiments, preferably, the solvent used in the halogen atom transfer radical addition reaction is n-hexane or dichloromethane, and n-hexane is more preferably used.

[0051] There is no special requirement for the amount of the solvent, as long as the raw materials are dissolved or dispersed uniformly.

[0052] In some embodiments, the molar ratio of the olefin compound 1 to the base is 1.0:(1.0-1.5).

[0053] In some embodiments, preferably, the molar ratio of the olefin compound 1 to the base is 1.0:1.2.

[0054] Wherein, the base exists in the form of a solution, the solvent is preferably tetrahydrofuran, and the concentration of the base in the solution is 1.5M~3.5M, preferably 2.5M.

[0055] In some embodiments, the deprotonated intramolecular cyclization reaction has a reaction temperature of -20°C to 10°C; the deprotonated intramolecular cyclization reaction is carried out under the protection of an inert gas.

[0056] In some embodiments, preferably, the deprotonation intramolecular cyclization reaction has a reaction temperature of 0°C.

[0057] Wherein, the inert gas is preferably nitrogen.

[0058] Beneficial effects:

[0059] (1) The present invention forms a γ-iodine-substituted geminal di(boryl) ester compound intermediate through an intermolecular halogen atom transfer free radical addition reaction, and then the γ-iodine-substituted geminal di(boryl) ester compound intermediate is deprotonated and alkylated in the presence of a base to produce a cyclization product, a geminal bis(boryl) cyclopropane compound. The method provided by the present invention can synthesize geminal bis(boryl) cyclopropane compounds in one pot from olefins combined with (diborylmethyl) iodide under visible light irradiation, is simple to operate, and provides a rapid way to synthesize highly functionalized compound molecules.

[0060] (2) The photoinduced technology provided by the present invention exhibits good functional group tolerance and obtains a wide range of geminal bis(boryl)cyclopropane compounds, which have potential application value in the field of organic synthesis. Furthermore, derivatization experiments have proved that geminal bis(boryl)cyclopropane compounds can be used to synthesize highly functionalized compound molecules.

[0061] (3) The reagents used in the preparation method of the present invention are stable in nature, easy to prepare and simple to operate. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments, and the above and / or other advantages of the present invention will become more clear.

[0063] Figure 1 NMR of product 3a 1 H NMR spectra.

[0064] Figure 2 NMR of product 3a 13 C NMR spectrum.

[0065] Figure 3 NMR of product 3a 11 B NMR spectrum. DETAILED DESCRIPTION

[0066] The present invention can be better understood according to the following examples. However, it is easy for those skilled in the art to understand that the contents described in the examples are only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.

[0067] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0068] The yield of the geminal bis(boryl)cyclopropane-containing product in the examples of the present invention is the isolated yield, which is calculated by weighing.

[0069] The present invention is used in the practice of It can be purchased commercially or prepared by referring to the existing technology (HuJ, Tang M, Wang J, et al. Photocatalyzed Borylcyclopropanation of Alkeneswith a (Diborylmethyl)iodide Reagent[J]).

[0070] Embodiment 1:

[0071] ;

[0072] In a furnace-dried sample bottle equipped with a magnetic stir bar under nitrogen atmosphere, olefin compound 1a (0.30 mmol, 1.0 equiv.), (diboronmethyl) iodide 2 (0.36 mmol, 1.2 equiv.), Mn 2 (CO) 10 (0.030mmol, 10 mol%) and n-hexane (1 mL). The vial was then sealed with a rubber cap, and the mixture was irradiated with a blue 440 nm LED lamp (power 25 W) and stirred at 25℃~40℃ for 3 hours for halogen atom transfer radical addition reaction. After the reaction was completed, the reaction mixture was cooled to -20℃, and lithium diisopropylamide (LDA, dosage 1.2 equiv.; dissolved in tetrahydrofuran, concentration 2.5 M) was added, and then stirred for 2 hours under nitrogen protection at 0℃ for deprotonation intramolecular cyclization reaction. After the reaction was completed, the crude reaction product was filtered, concentrated under reduced pressure, and separated by silica gel column chromatography to obtain geminal bis(boryl)cyclopropane product 3a, a colorless oily liquid, with an isolated yield of 81%.

[0073] The NMR, mass spectrometry and infrared data of product 3a are as follows: 1 H NMR (300 MHz, CDCl 3 ): d 7.30 – 7.25(m, 2H), 7.23 – 7.15 (m, 3H), 2.86 – 2.69 (m, 2H), 1.89 – 1.71 (m, 1H), 1.61 – 1.50 (m, 1H), 1.41 – 1.27 (m, 1H), 1.26 (s, 6H), 1.23 (s, 6H), 1.21 (s,6H), 1.19 (s, 6H), 0.97 (dd, J = 7, 3 Hz, 1H), 0.68 (dd, J = 5, 3 Hz, 1H). 13CNMR (75 MHz, CDCl 3 ): d 142.6, 128.4, 128.1, 125.4, 82.9, 82.6, 36.1, 34.8,25.1, 24.8, 24.5, 24.3, 23.3, 15.8. 11 B NMR (96 MHz, CDCl 3 ): d 32.8. HRMS-ESI(m / z): Calculated (found) for C 23 H 37 B 2 O 4 [M+H] + 399.2872 (399.2867). IR (film):3054, 2982, 1370, 1317, 1266, 1138, 970, 850, 742, 704 cm -1 NMR of product 3a 1 H NMR spectra Figure 1 , NMR 13 C NMR spectra Figure 2 , NMR 11 B NMR diagram Figure 3 .

[0074] Embodiment 2:

[0075] ;

[0076] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1b, and finally geminal bis(boryl)cyclopropane product 3b is prepared as a colorless oily liquid with an isolated yield of 73%.

[0077] The NMR, mass spectrometry and infrared data of product 3b are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 1.57 – 1.51(m, 1H), 1.46 – 1.39 (m, 2H), 1.37 – 1.30 (m, 4H), 1.26 (s, 6H), 1.24 (s,6H), 1.20 (s, 6H), 1.19 (s, 6H), 1.16 – 1.08 (m, 1H), 0.95 – 0.87 (m, 5H), 0.65 (dd, J = 5, 3 Hz, 1H). 13C NMR (101 MHz, CDCl 3 ): d 82.9, 82.5, 32.9, 32,25.1, 24.8, 24.6, 24.3, 23.7, 22.6, 16, 14.1. 11 B NMR (128 MHz, CDCl 3 ): d 33.4.HRMS-ESI (m / z): Calculated (found) for C 20 H 39 B 2 O 4 [M+H] + 365.3029 (365.3020). IR(film): 3054, 2982, 1372, 1316, 1266, 1139, 969, 896, 849, 742, 705 cm -1 .

[0078] Embodiment 3:

[0079] ;

[0080] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1c, and finally geminal bis(boryl)cyclopropane product 3c is prepared as a colorless oily liquid with an isolated yield of 72%.

[0081] The NMR, mass spectrometry and infrared data of product 3c are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 7.37 – 7.29 (m,4H), 7.22 – 7.18 (m, 1H), 3.11 (dd, J = 15, 4 Hz, 1H), 2.28 (dd, J = 15, 10 Hz,1H), 1.53 – 1.44 (m, 1H), 1.27 (s, 6H), 1.26 (s, 6H), 1.21 (s, 6H), 1.20 (s,6H), 1.07 (dd, J = 5, 3 Hz, 1H), 0.90 (dd, J = 5, 3 Hz, 1H). 13 C NMR (101 MHz, CDCl 3 ): d142.2, 128.4, 128.2, 125.8, 83.1, 82.7, 38.8, 25.1, 24.8, 24.6,24.4, 24.1, 16.3. 11 B NMR (128 MHz, CDCl 3 ): d 33.1. HRMS-ESI (m / z): Calculated(found) for C 22 H 35 B 2 O 4 [M+H] + 385.2716 (385.2709). IR (film): 3052, 2980, 1371,1314, 1268, 896, 849, 742 cm -1 .

[0082] Embodiment 4:

[0083] ;

[0084] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1d, and finally geminal bis(boryl)cyclopropane product 3d is prepared as a colorless oily liquid with an isolated yield of 79%.

[0085] The NMR, mass spectrometry and infrared data of product 3d are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 1.74 – 1.67 (m,1H), 1.56 – 1.50 (m, 1H), 1.31 (d, J = 3 Hz, 1H), 1.26 (s, 6H), 1.23 (s, 6H), 1.20 (s, 6H), 1.19 (s, 6H), 0.99 – 0.95 (m, 1H), 0.94 (d, J = 7 Hz, 3H), 0.91(d, J = 7 Hz, 3H), 0.86 (d, J = 7 Hz, 1H), 0.67 (dd, J = 5, 3 Hz, 1H). 13 C NMR (101MHz, CDCl 3 ): d82.9, 82.5, 42.2, 28.8, 25.1, 24.8, 24.5, 24.3, 22.9, 22.3,22.1, 16.5. 11 B NMR (128 MHz, CDCl 3 ): d 33.5. HRMS-ESI (m / z): Calculated (found)for C 19 H 37 B 2 O 4 [M+H] + 351.2872 (351.2865). IR (film): 3050, 2982, 1372, 1268,896, 742 cm -1 .

[0086] Embodiment 5:

[0087] ;

[0088] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1e, and finally geminal bis(boryl)cyclopropane product 3e is prepared as a colorless oily liquid with an isolated yield of 69%.

[0089] The NMR, mass spectrometry and infrared data of product 3e are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 1.99 – 1.89 (m,1H), 1.83 – 1.75 (m, 1H), 1.74 – 1.67 (m, 2H), 1.64 – 1.58 (m, 1H), 1.30 –1.27 (m, 2H), 1.26 (s, 6H), 1.24 (s, 6H), 1.20 (s, 6H), 1.18 (s, 6H), 1.13 –1.06 (m, 3H), 1.05 – 0.97 (m, 1H), 0.90 (dd, J = 7, 3 Hz, 1H), 0.70 (dd, J = 5, 3Hz, 2H). 13 C NMR (101 MHz, CDCl 3 ): d82.8, 82.5, 41.8, 33.7, 33.3, 31, 26.6,26.4, 26.1, 25.1, 24.8, 24.5, 24.3, 14.8. 11 B NMR (128 MHz, CDCl 3 ): d 34.2. HRMS-ESI (m / z): Calculated (found) for C 21 H 39 B 2 O 4 [M+H] + 377.3029 (377.3023). IR(film): 2979, 2929, 2854, 1380, 1371, 1320, 1269, 1166, 1138, 970, 909, 850,734 cm -1 .

[0090] Embodiment 6:

[0091] ;

[0092] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1f, and finally geminal bis(boryl)cyclopropane product 3f is prepared as a colorless oily liquid with an isolated yield of 67%.

[0093] The NMR, mass spectrometry and infrared data of product 3f are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 1.29 (s, 6H), 1.27 (s, 6H), 1.20 (s, 6H), 1.19 (s, 6H), 0.91 (s, 9H), 0.89 – 0.86 (m, 1H), 0.79 – 0.73 (m, 2H). 13 C NMR (101 MHz, CDCl 3 ): d 83, 82.7, 36.1, 30.9, 28.8,25, 24.9, 24.6, 24.5, 10.7. 11 B NMR (128 MHz, CDCl 3 ): d 31.9. HRMS-ESI (m / z):Calculated (found) for C 19 H37 B 2 O 4 [M+H] + 351.2872 (351.2866). IR (film): 2972,2850, 1378, 1316, 1270, 970, 850 cm -1 .

[0094] Embodiment 7:

[0095] ;

[0096] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1g, and finally 3g of geminal bis(boryl)cyclopropane product is prepared as a white solid with an isolated yield of 74%.

[0097] The NMR, mass spectrometry and infrared data of product 3g are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 7.24 – 7.15(m, 2H), 6.85 – 6.80 (m, 2H), 3.78 (s, 3H), 3.01 (dd, J = 15, 4 Hz, 1H), 2.19(dd, J = 15, 10 Hz, 1H), 1.45 – 1.38 (m, 1H), 1.24 (s, 6H), 1.22 (s, 6H), 1.18 (s, 6H), 1.16 (s, 6H), 1.03 (dd, J = 7, 3 Hz, 1H), 0.84 (dd, J = 5, 3 Hz, 1H). 13 CNMR (101 MHz, CDCl 3 ): d 157.7, 134.4, 129.2, 113.6, 83, 82.6, 55.2, 37.9,25.1, 24.7, 24.5, 24.3, 16.2. 11 B NMR (128 MHz, CDCl 3 ): d 33.4. HRMS-ESI (m / z):Calculated (found) for C 23 H 37 B 2 O 5 [M+H]+ 415.2822 (415.2814). IR (film): 3055,2982, 1636, 1422, 1381, 1317, 1266, 1189, 1139, 896, 849, 738, 705, 665 cm -1 .

[0098] Embodiment 8:

[0099] ;

[0100] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1h, and finally geminal bis(boryl)cyclopropane product 3h is prepared as a colorless oily liquid with an isolated yield of 83%.

[0101] The NMR, mass spectrometry and infrared data of product 3h are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 7.29 (t, J = 8 Hz, 2H), 6.97 – 6.88 (m, 3H), 4.00 (t, J = 7 Hz, 2H), 2.04 – 1.87 (m, 2H), 1.72 –1.63 (m, 1H), 1.49 – 1.33 (m, 2H), 1.27 (s, 6H), 1.25 (s, 6H), 1.21 (s, 6H), 1.20 (s, 6H), 0.98 (dd, J = 7, 3 Hz, 1H), 0.70 (dd, J = 5, 3 Hz, 1H). 13 C NMR (101MHz, CDCl 3 ): d 159.1, 129.3, 120.3, 114.4, 82.9, 82.6, 67.5, 29.47, 29.45,25.1, 24.8, 24.7, 24.6, 24.3, 23.1, 15.8. 11 B NMR (128 MHz, CDCl 3 ): d 32.9.HRMS-ESI (m / z): Calculated (found) for C 24 H 39 B 2 O 5[M+H] + 429.2978 (429.2971). IR(film): 3447, 3054, 2985, 1636, 1422, 1317, 1265, 1140, 896, 741, 705 cm -1 .

[0102] Embodiment 9:

[0103] ;

[0104] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1i, and finally geminal bis(boryl)cyclopropane product 3i is prepared as a colorless oily liquid with an isolated yield of 77%.

[0105] The NMR, mass spectrometry and infrared data of product 3i are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 7.39 – 7.31 (m,4H), 7.30 – 7.24 (m, 1H), 4.55 (s, 2H), 3.73 (dd, J = 10, 5 Hz, 1H), 3.20 (dd, J = 10, 8 Hz, 1H), 1.63 – 1.53 (m, 1H), 1.22 (s, 6H), 1.20 (s, 6H), 1.19 (s,6H), 1.18 (s, 6H), 1.05 (dd, J = 7, 3 Hz, 1H), 0.84 (dd, J = 5, 3 Hz, 1H). 13 C NMR (101 MHz, CDCl 3 ): d 138.6, 128.3, 127.8, 127.4, 83.0, 82.8, 72.7, 72.5, 24.9,24.8, 24.7, 24.6, 24.4, 22.0, 14.6. 11 B NMR (128 MHz, CDCl 3 ): d 33.8. HRMS-ESI(m / z): Calculated (found) for C 23 H 37 B 2 O 5 [M+H]+ 415.2822 (415.2815). IR (film):3056, 2981, 1634, 1412, 1320, 1268, 1140, 894, 721 cm -1 .

[0106] Embodiment 10:

[0107] ;

[0108] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1j, and finally geminal bis(boryl)cyclopropane product 3j is prepared as a colorless oily liquid with an isolated yield of 75%.

[0109] The NMR, mass spectrometry and infrared data of product 3j are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 6.97 – 6.92(m, 2H), 6.82 – 6.79 (m, 2H), 3.89 (t, J = 7 Hz, 2H), 1.82 – 1.75 (m, 2H), 1.60 – 1.56 (m, 2H), 1.23 (s, 6H) 1.22 – 1.20 (m, 3H), 1.20 (s, 6H), 1.17 (s,12H), 0.94 (dd, J = 7, 3 Hz, 1H), 0.69 – 0.60 (m, 1H). 13 C NMR (101 MHz, CDCl 3 ): d 158.3, 155.9, 155.2, 115.8, 115.6, 115.4, 115.3, 82.9, 82.6, 68.6, 32.8,29.2, 26.3, 25.1, 24.8, 24.6, 24.3, 23.4, 16. 19 F NMR (376 MHz, CDCl 3 ) δ -124.6. 11 B NMR (128 MHz, CDCl 3 ): d 31.8. HRMS-ESI (m / z): Calculated (found) forC 25 H 40 B2 FO 5 [M+H] + 461.3040 (461.3036). IR (film): 2980, 2932, 1507, 1471, 1445,1380, 1372, 1316, 1266, 1249, 1213, 1167, 1139, 1097, 969, 910, 849, 829,734, 649, 514 cm -1 .

[0110] Embodiment 11:

[0111] ;

[0112] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1k, and finally geminal bis(boryl)cyclopropane product 3k is prepared as a colorless oily liquid with an isolated yield of 76%.

[0113] The NMR, mass spectrometry and infrared data of product 3k are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 3.58 (t, J = 7.2Hz, 2H), 2.01 – 1.86 (m, 2H), 1.69 – 1.57 (m, 1H), 1.44 – 1.27 (m, 2H), 1.26(s, 6H), 1.24 (s, 6H), 1.19 (s, 12H), 0.96 (dd, J = 7, 3 Hz, 1H), 0.68 (dd, J =5, 3 Hz, 1H). 13 C NMR (101 MHz, CDCl 3 ): d 83.0, 82.7, 45.0, 32.8, 30.3, 25.1,24.8, 24.6, 24.3, 22.5, 15.8. 11 B NMR (128 MHz, CDCl 3 ): d 31.7. HRMS-ESI (m / z):Calculated (found) for C 18 H 34 B 2 C1O 4 [M+H] +371.2326 (371.2321). IR (film): 2978,2931, 1444, 1371, 1316, 1269, 1214, 1166, 1139, 969, 849 cm -1 .

[0114] Embodiment 12:

[0115] ;

[0116] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 11, and finally geminal bis(boryl)cyclopropane product 31 is prepared as a colorless oily liquid with an isolated yield of 78%.

[0117] The NMR, mass spectrometry and infrared data of product 3l are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 7.36 (d, J = 9 Hz,2H), 6.77 (d, J = 9 Hz, 2H), 3.91 (t, J = 7 Hz, 2H), 1.83 – 1.77 (m, 2H), 1.62 –1.58 (m, 2H), 1.28 (t, J = 6 Hz, 1H), 1.27 – 1.24 (m, 2H), 1.25 (s, 6H), 1.22(s, 6H), 1.20 (s, 6H), 1.18 (s, 6H), 0.98 – 0.94 (m, 1H), 0.67 (dd, J = 5, 3Hz, 1H). 13 C NMR (101 MHz, CDCl 3 ): d 158.2, 132.2, 116.3, 112.5, 82.9, 82.6,68.3, 32.8, 29.0, 26.2, 25.1, 24.8, 24.6, 24.3, 23.4, 16. 11 B NMR (128 MHz, CDCl 3 ): d 33.5. HRMS-ESI (m / z): Calculated (found) for C 25 H 40 B 2 B O 5 [M+H]+ 521.2240(521.2237). IR (film): 2977, 1596, 1505, 1378, 1372, 1327, 1265, 1229, 1137,968, 845, 788, 671, 579 cm -1 .

[0118] Embodiment 13:

[0119] ;

[0120] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1m, and finally geminal bis(boryl)cyclopropane product 3m is prepared as a colorless oily liquid with an isolated yield of 71%.

[0121] The NMR, mass spectrometry and infrared data of product 3m are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 7.55 (d, J = 9Hz, 2H), 6.68 (d, J = 9 Hz, 2H), 3.92 (t, J = 7 Hz, 2H), 1.84 – 1.78 (m, 2H), 1.62 – 1.58 (m, 2H), 1.32 – 1.27 (m, 3H), 1.26 (s, 6H), 1.23 (s, 6H), 1.20 (s, 6H), 1.19 (s, 6H), 0.96 (dd, J = 7, 3 Hz, 1H), 0.67 (dd, J = 5, 3 Hz, 1H). 13 CNMR (101 MHz, CDCl 3 ): d 159.0, 138.1, 116.9, 82.9, 82.6, 68.1, 32.8, 29.0,26.2, 25.1, 24.8, 24.6, 24.3, 23.4, 16. 11 B NMR (128 MHz, CDCl 3 ): d 31.5. HRMS-ESI (m / z): Calculated (found) for C 25 H 40 B 2 IO5 [M+H] + 569.2101 (569.2093). IR(film): 2981, 2252, 1587, 1487, 1471, 1380, 1372, 1315, 1243, 1175, 1139,968, 908, 849, 822, 734, 650cm -1 .

[0122] Embodiment 14:

[0123] ;

[0124] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1n, and finally geminal bis(boryl)cyclopropane product 3n is prepared as a colorless oily liquid with an isolated yield of 74%.

[0125] The NMR, mass spectrometry and infrared data of product 3n are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 7.54 (d, J = 9Hz, 2H), 6.95 (d, J = 9 Hz, 2H), 4.02 – 3.97 (m, 2H), 1.87 – 1.77 (m, 2H), 1.68 – 1.54 (m, 2H), 1.33 – 1.26 (m, 3H), 1.25 (s, 6H), 1.23 (s, 6H), 1.20 (s, 6H), 1.19 (s, 6H), 1.00 – 0.94 (m, 1H), 0.68 (dd, J = 5, 3 Hz, 1H). 13 C NMR (101MHz, CDCl 3 ): d 161.6, 133.4, 127.5, 126.8, 126.8, 126.7, 125.9, 123.2, 114.4,82.9, 82.6, 68.2, 32.7, 28.9, 26.2, 25.1, 24.8, 24.6, 24.3, 23.4, 16. 11 B NMR (128 MHz, CDCl 3 ): d 33.1. HRMS-ESI (m / z): Calculated (found) for C26 H 40 B 2 F 3 O 5 [M+H] + 511.3008 (511.3002). IR (film): 2982, 1721, 1636, 1381, 1372, 1313, 1266,1222, 1168, 1138, 1018, 969, 896, 849, 739, 705 cm -1 .

[0126] Embodiment 15:

[0127] ;

[0128] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1o, and finally geminal bis(boryl)cyclopropane product 3o is prepared as a colorless oily liquid with an isolated yield of 62%.

[0129] The NMR, mass spectrometry and infrared data of product 3o are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 3.61 (s, 3H),1.61 – 1.47 (m, 2H), 1.45 – 1.31 (m, 2H), 1.21 (s, 24H), 1.12 – 1.03 (m, 1H),0.85 (t, J = 8 Hz, 1H), 0.77 – 0.69 (m, 1H). 13 C NMR (101 MHz, CDCl 3 ): d 175.0,83.1, 83.1, 51.4, 29.0, 25.3, 24.8, 24.6, 24.5, 20.1, 16.0. 11 B NMR (128 MHz, CDCl 3 ): d 33.0. HRMS-ESI (m / z): Calculated (found) for C 19 H 35 B 2 O 6 [M+H] +381.2614(381.2611). IR (film): 2983, 2256, 1732, 1641, 1423, 1371, 1314, 1262, 1214,1141, 906, 732, 649 cm -1 .

[0130] Embodiment 16:

[0131] ;

[0132] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1p, and finally geminal bis(boryl)cyclopropane product 3p is prepared as a colorless oily liquid with an isolated yield of 68%.

[0133] The NMR, mass spectrometry and infrared data of product 3p are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 5.82 – 5.53 (m,2H), 2.30 – 1.86 (m, 5H), 1.47 – 1.39 (m, 1H), 1.26 (s, 6H), 1.23 (s, 6H),1.21 (s, 6H), 1.19 (s, 6H), 1.14 – 1.06 (m, 1H), 1.06 – 0.96 (m, 1H), 0.94(dd, J = 7, 3 Hz, 1H), 0.78 – 0.69 (m, 1H). 13 C NMR (101 MHz, CDCl 3 ): d 126.9,126.7, 126.6, 126.5, 82.9, 82.8, 82.6, 37.9, 37.7, 32.1, 31.9, 30.2, 30.0,29.3, 28.8, 25.0, 24.8, 24.5, 24.4, 24.2, 14.8, 14.6. 11 B NMR (128 MHz, CDCl 3 ): d 33.5. HRMS-ESI (m / z): Calculated (found) for C 21 H 37 B 2 O 4 [M+H] +375.2872(375.2865). IR (film): 3056, 2972, 1702, 1420, 1266, 1138, 894, 731, 705 cm -1 .

[0134] Embodiment 17:

[0135] ;

[0136] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1q, and finally geminal bis(boryl)cyclopropane product 3q is prepared as a colorless oily liquid with an isolated yield of 75%.

[0137] The NMR, mass spectrometry and infrared data of product 3q are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 7.65 – 7.55(m, 2H), 7.46 – 7.31 (m, 3H), 3.85 – 3.58 (m, 2H), 1.88 – 1.78 (m, 1H), 1.45 – 1.37 (m, 1H), 1.33 – 1.27 (m, 1H), 1.24 (s, 6H), 1.22 (s, 6H), 1.20 (s, 6H), 1.18 (s, 6H), 0.92 (dd, J = 7, 3 Hz, 1H), 0.65 (dd, J = 5, 3 Hz, 1H), 0.39(s, 6H). 13 C NMR (101 MHz, CDCl 3 ): d 138.2, 133.5, 129.4, 127.8, 82.9, 82.6,63.3, 36, 25.1, 24.8, 24.7, 24.6, 24.4, 20, 15.5, -1.57, -1.64. 11 BNMR (128MHz, CDCl 3 ): d 33.5. HRMS-ESI (m / z): Calculated (found) for C 25 H 43 B 2 O 5 Si [M+H] +473.3060 (473.3054). IR (film): 3056, 1703, 1264, 896, 739, 705 cm -1 .

[0138] Embodiment 18:

[0139] ;

[0140] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1r, and finally geminal bis(boryl)cyclopropane product 3r is prepared as a colorless oily liquid with an isolated yield of 70%.

[0141] The NMR, mass spectrometry and infrared data of product 3r are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 8.09 (d, J = 8Hz, 1H), 7.87 (d, J = 8 Hz, 1H), 7.73 (d, J = 8 Hz, 1H), 7.57 (d, J = 7 Hz, 1H),7.53 – 7.45 (m, 3H), 3.62 (dd, J = 15, 4 Hz, 1H), 2.78 – 2.68 (m, 1H), 1.33 –1.28 (m, 1H), 1.26 (s, 6H), 1.24 (s, 6H), 1.23 (s, 6H), 1.22 (s, 6H), 1.11(dd, J = 7, 3 Hz, 1H), 0.96 (dd, J = 5, 3 Hz, 1H). 13 C NMR (101 MHz, CDCl 3 ): d 138.2, 133.7, 132.1, 128.6, 126.4, 125.68, 125.65, 125.4, 125.3, 123.8, 83.1,82.8, 35.2, 25.1, 24.8, 24.6, 24.4, 23.1, 16.8. 11 B NMR (128 MHz, CDCl 3 ): d33.4. HRMS-ESI (m / z): Calculated (found) for C 26 H 37 B 2 O 4 [M+H] + 435.2872(435.2865). IR (film): 3447, 2977, 1379, 1370, 1314, 1138, 849, 798, 790,777, 671, 579, 433, 422 cm -1 .

[0142] Embodiment 19:

[0143] ;

[0144] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1s, and finally geminal bis(boryl)cyclopropane product 3s is prepared as a white solid with an isolated yield of 63%.

[0145] The NMR, mass spectrometry and infrared data of product 3s are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 8.13 (t, J = 8 Hz,2H), 7.47 (q, J = 8 Hz, 4H), 7.28 – 7.21 (m, 2H), 4.46 – 4.25 (m, 2H), 2.12 –2.01 (m, 1H), 1.67 – 1.54 (m, 1H), 1.50 – 1.32 (m, 3H), 1.21 (s, 6H), 1.20(s, 6H), 1.16 (s, 6H), 1.11 (s, 6H), 1.01 – 0.94 (m, 1H), 0.67 – 0.59 (m,1H). 13 C NMR (101 MHz, CDCl 3 ): d 140.4, 125.5, 122.8, 120.3, 118.6, 108.8, 82.9,82.7, 42.9, 30.7, 29.3, 25.0, 24.8, 24.6, 24.2, 23.1, 15.7. 11 B NMR (128 MHz, CDCl 3 ): d31.9. HRMS-ESI (m / z): Calculated (found) for C 30 H 42 B 2 NO 4 [M+H] + 502.3294(502.3289). IR (film): 2978, 1725, 1703, 1607, 1518, 1469, 1371, 1309, 1242,1200, 1139, 1083, 968, 849, 737, 703 cm -1 .

[0146] Embodiment 20:

[0147] ;

[0148] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1t, and finally geminal bis(boryl)cyclopropane product 3t is prepared as a colorless oily liquid with an isolated yield of 58%.

[0149] The NMR, mass spectrometry and infrared data of product 3t are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 7.52 (d, J = 8Hz, 1H), 7.35 (s, 1H), 7.12 – 7.02 (m, 2H), 6.46 (d, J = 3 Hz, 1H), 4.18 –4.04 (m, 2H), 2.06 – 1.92 (m, 2H), 1.61 – 1.47 (m, 1H), 1.25 – 1.23 (m, 2H), 1.20 (s, 12H), 1.19 (s, 6H), 1.16 (s, 6H), 0.97 (dd, J = 7, 3 Hz, 1H), 0.64(dd, J = 5, 3 Hz, 1H). 13 C NMR (101 MHz, CDCl 3 ): d 136.4, 128.4, 127.3, 127.0,121.7, 119.8, 109.4, 101.2, 83, 82.7, 46.3, 30.5, 30.4, 25.1, 24.8, 24.6,24.3, 22.8, 15.7.11 B NMR (128 MHz, CDCl 3 ): d 33.3. HRMS-ESI (m / z): Calculated(found) for C 26 H 39 B 2 ClNO 4 [M+H] + 486.2748 (486.2742). IR (film): 3056, 2982,2302, 1421, 1368, 1312, 1261, 1142, 895, 739, 704 cm -1 .

[0150] Embodiment 21:

[0151] ;

[0152] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1u, and finally geminal bis(boryl)cyclopropane product 3u is prepared as a colorless oily liquid with an isolated yield of 78%.

[0153] The NMR, mass spectrometry and infrared data of product 3u are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 3.66 – 3.52 (m,1H), 3.32 – 3.19 (m, 1H), 3.03 – 2.88 (m, 1H), 2.32 – 2.14 (m, 2H), 2.12 –1.99 (m, 1H), 1.94 – 1.82 (m, 1H), 1.75 – 1.48 (m, 6H), 1.39 – 1.29 (m, 1H), 1.22 (s, 6H), 1.20 (s, 6H), 1.16 (s, 6H), 1.15 (s, 6H), 0.97 – 0.81 (m, 10H), 0.78 – 0.71 (m, 3H), 0.67 – 0.58 (m, 1H). 13 C NMR (101 MHz, CDCl 3 ): d82.9,82.6, 78.9, 78.8, 68.4, 68.2, 48.3, 40.5, 35.2, 34.7, 31.6, 30.6, 29.8, 29.8,25.5, 25.1, 24.8, 24.6, 24.6, 24.6, 24.5, 24.3, 23.5, 23.3, 22.4, 21.3, 21.0,16.2, 16.2, 16.0, 15.9. 11 B NMR (128 MHz, CDCl 3 ): d 33.3. HRMS-ESI (m / z):Calculated (found) for C 28 H 53 B 2 O 5 [M+H] + 491.4074 (491.4069). IR (film): 2981,1769, 1373, 1324, 1266, 1247, 1169, 1138, 968, 848, 738, 704 cm -1 .

[0154] Embodiment 22:

[0155] ;

[0156] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1v, and finally geminal bis(boryl)cyclopropane product 3v is prepared as a colorless oily liquid with an isolated yield of 63%.

[0157] The NMR, mass spectrometry and infrared data of product 3v are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 4.37 (q, J= 7Hz, 1H), 3.54 – 3.30 (m, 4H), 3.24 – 3.05 (m, 1H), 1.99 – 1.93 (m, 1H), 1.91– 1.77 (m, 3H), 1.76 – 1.72 (m, 1H), 1.70 – 1.55 (m, 10H), 1.53 – 1.43 (m,3H), 1.43 – 1.29 (m, 3H), 1.28 – 1.24 (m, 4H), 1.22 (s, 6H), 1.19 (s, 6H),1.16 (s, 6H), 1.14 (s, 6H), 1.12 – 0.98 (m, 4H), 0.94 (d, J = 7 Hz, 3H), 0.92 –0.84 (m, 3H), 0.81 – 0.72 (m, 9H), 0.66 – 0.57 (m, 2H). 13 C NMR (101 MHz,CDCl 3 ): d 109.2, 82.9, 82.6, 80.9, 78.3, 67.6, 66.8, 62.2, 56.3, 54.4, 44.9,41.6, 40.6, 40.1, 37.0, 35.9, 35.1, 34.9, 32.3, 31.8, 31.4, 30.4, 30.3, 29.7,28.8, 28.8, 28.3, 25.1, 24.8, 24.7, 24.6, 24.3, 23.3, 21.0, 17.1, 16.5, 16,14.5, 12.3. 11 B NMR (128 MHz, CDCl 3 ): d 32.5. HRMS-ESI (m / z): Calculated(found) for C 45 H 77 B 2 O 5 [M+H] + 750.6952 (750.6949). IR (film): 2981, 1769, 1373,1324, 1266, 1247, 1169, 1138, 968, 848, 738, 704 cm -1 。

[0158] Example 23:

[0159] ;

[0160] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1w, and finally geminal bis(boryl)cyclopropane product 3w is prepared as a colorless oily liquid with an isolated yield of 66%.

[0161] The NMR, mass spectrometry and infrared data of product 3w are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 5.86 (d, J = 4Hz, 1H), 4.51 (s, 1H), 4.30 (q, J = 7 Hz, 1H), 4.15 – 4.02 (m, 2H), 3.96 (t, J =7 Hz, 1H), 3.83 (d, J = 3 Hz, 1H), 3.63 – 3.53 (m, 1H), 3.53 – 3.42 (m, 1H), 2.29 – 1.96 (m, 1H), 1.62 – 1.51 (m, 2H), 1.48 (s, 3H), 1.41 (s, 3H), 1.34(s, 3H), 1.31 (s, 3H), 1.24 (s, 2H) 1.22 (s, 6H), 1.20 (s, 6H), 1.19 – 1.16(m, 2H), 1.17 (s, 6H), 1.15 (s, 6H), 0.91 (dd, J = 7, 3 Hz, 1H), 0.69 – 0.54(m, 1H). 13 C NMR (101 MHz, CDCl 3 ): d 111.6, 108.8, 105.3, 82.9, 82.7, 82.5,82.0, 81.2, 72.5, 70.7, 67.2, 32.8, 32.7, 29.7, 29.6, 29.5, 26.8, 26.8, 26.2,25.4, 25.1, 24.9, 24.83, 24.76, 24.7, 24.54, 24.46, 24.3, 23.4, 16.0. 11 B NMR (128 MHz, CDCl 3 ): d32.6. HRMS-ESI (m / z): Calculated (found) for C 31 H 55 B 2 O 10 [M+H] + 608.4305(608.4298). IR (film): 2982, 1654, 1373, 1317, 1266, 1215, 1166,1138, 1080, 1019, 968, 849, 735, 705 cm -1 .

[0162] Embodiment 24:

[0163] ;

[0164] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1x, and finally geminal bis(boryl)cyclopropane product 3x is prepared as a colorless oily liquid with an isolated yield of 49%.

[0165] The NMR, mass spectrometry and infrared data of product 3x are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 3.94 – 3.87 (m,2H), 3.86 – 3.82 (m, 2H), 3.44 (td, J = 7, 3Hz, 2H), 3.16 (tt, J = 11, 5 Hz, 1H),1.99 – 1.93 (m, 1H), 1.82 – 1.48 (m, 12H), 1.42 – 1.31 (m, 5H), 1.28 – 1.24(m, 4H), 1.22 (s, 6H), 1.20 (s, 6H), 1.23 – 1.18 (m, 6H), 1.17 (s, 6H), 1.15 (m, 1H), 0.92 (m, 2H), 0.89 – 0.85 (m, 1H), 0.82 (s, 3H), 0.78 (s, 3H), 0.71– 0.60 (m, 2H). 13 C NMR (101 MHz, CDCl 3 ): d119.5, 82.9, 82.5, 78.2, 67.6,65.2, 64.5, 54.2, 50.7, 46.0, 44.9, 37.1, 35.8, 35.7, 34.9, 34.2, 31.4, 30.7,30.3, 29.6, 28.7, 28.3, 25.1, 24.8, 24.7, 24.5, 24.3, 23.3, 22.6, 20.6, 16.0,14.4, 12.33. 11 B NMR (128 MHz, CDCl 3 ): d 33.2. HRMS-ESI (m / z): Calculated(found) for C 39 H 67 B 2 O 7 [M+H] + 669.5067 (669.5064). IR (film): 2982, 1654, 1373,1317, 1266, 1215, 1166, 1138, 1080, 1019, 968, 849, 735, 705 cm -1 .

[0166] Embodiment 25:

[0167] ;

[0168] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1y, and finally geminal bis(boryl)cyclopropane product 3y is prepared as a colorless oily liquid with an isolated yield of 71%.

[0169] The NMR, mass spectrometry and infrared data of product 3y are as follows: 1 H NMR (400 MHz, CDCl 3 ): d 3.63 (t, J = 7Hz, 2H), 2.56 (t, J = 7 Hz, 2H), 2.14 (s, 3H), 2.10 (s, 3H), 2.07 (s, 3H), 1.93(m, 2H), 1.83 – 1.68 (m, 5H), 1.52 (p, J = 7 Hz, 4H), 1.36 (m, 7H), 1.28 (dd, J=6, 4 Hz, 5H), 1.24 (s, 6H), 1.22 (s, 6H), 1.19 (s, 6H), 1.17 (s, 6H), 1.16 –1.01 (m, 8H), 0.96 (dd, J = 7, 2 Hz, 1H), 0.90 – 0.80 (m, 14H), 0.69 (dd, J = 5,3 Hz, 1H). 13 C NMR (101 MHz, CDCl 3 ): d 14.8, 24.6, 24.5, 24.4, 23.9, 23.5,22.74, 22.65, 21.1, 20.7, 19.8, 19.7, 16.0, 12.7, 11.9, 11.8. 11 B NMR (128MHz, CDCl 3 ): d 32.7. HRMS-ESI (m / z): Calculated (found) for C 48 H 85 B 2 O 6 [M+H] + 779.6527 (779.6539). IR (film): 2929, 1460, 1380, 1319, 1265, 1249, 1139,1088, 969, 849, 741 cm -1 .

[0170] Embodiment 26:

[0171] ;

[0172] The preparation method is the same as that of Example 1, except that compound 1a is replaced by compound 1z, and finally geminal bis(boryl)cyclopropane product 3z is prepared as a colorless oily liquid with an isolated yield of 51%.

[0173] The NMR, mass spectrometry and infrared data of product 3z are as follows: 1H NMR (400 MHz, CDCl 3 ): d 5.35 (d, J = 6Hz, 1H), 4.42 (q, J = 7 Hz, 1H), 4.28 – 4.16 (m, 1H), 3.55 – 3.42 (m, 3H), 3.39(t, J = 11 Hz, 1H), 3.12 (m, 1H), 2.37 (dd, J = 13, 3 Hz, 1H), 2.22 – 2.14 (m,1H), 2.10 – 1.94 (m, 4H), 1.92 – 1.83 (m, 5H), 1.81 – 1.76 (m, 2H), 1.70 –1.58 (m, 7H), 1.57 – 1.37 (m, 6H), 1.29 – 1.27 (m, 2H), 1.26 (s, 6H), 1.24(s, 6H), 1.23 (s, 6H), 1.22 (s, 6H), 1.15 – 1.10 (m, 2H), 1.03 (s, 3H), 0.99(d, J = 7 Hz, 3H), 0.80 (t, J = 3 Hz, 6H). 13 C NMR (101 MHz, CDCl 3 ): d 141.1,121.1, 109.3, 83.2, 83.1, 80.8, 78.9, 67.0, 66.8, 62.1, 56.5, 50.1, 43.8,41.6, 40.2, 39.8, 39.1, 37.3, 37.2, 37.0, 36.7, 32.1, 31.8, 31.4, 31.3, 30.4,30.3, 28.8, 28.4, 24.9, 24.9, 24.7, 24.5, 24.4, 20.8, 19.4, 17.1, 16.3,14.5. 11 B NMR (128 MHz, CDCl 3 ): d 32.4. HRMS-ESI (m / z): Calculated (found) forC 45 H 75 B 2 O 7[M+H] + 749.5693 (749.5655). IR (film): 2977, 2932, 2248, 1456, 1371,1319, 1270, 1214, 1140, 1096, 1051, 1007, 969, 910, 864, 848, 734, 671, 647,578 cm -1 .

[0174] Example 27: Derivatization Experiment

[0175] ;

[0176] In an argon-filled glove box, compound 3a (0.30 mmol, 1.0 equiv), KO t Bu (0.45 mmol, 1.5 equivalents) and mesitylene (1 mL) were added, and the reaction mixture was stirred at 50 °C for 12 hours. The reaction progress was monitored by TLC thin layer chromatography. After the reaction was completed, the mixture was filtered through diatomaceous earth, washed with dichloromethane, and the combined organic phase was washed with Na 2 SO 4 After drying and then concentrating in vacuo, the crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate = 50 / 1) to obtain the corresponding product 4a as a colorless oil with an isolated yield of 87%.

[0177] The NMR data of product 4a are: 1 H NMR (300 MHz, CDCl 3 ) d 7.31 – 7.26 (m, 2H), 7.25 –7.15 (m, 3H), 2.79 – 2.68 (m, 2H), 1.63 – 1.56 (m, 2H), 1.26 (s, 6H), 1.25(s, 6H), 1.05 – 0.91 (m, 1H), 0.65 – 0.77 (m, 1H), 0.48 – 0.41 (m, 1H), -0.42– 0.31 (m, 1H). 13 C NMR (75 MHz, CDCl 3 ) d 142.5, 128.5, 128.2, 125.6, 82.8, 37.3,36.0, 24.7, 24.7, 18.0, 11.5. 11 B NMR (96 MHz, CDCl 3 ) d 32.9. The NMR data of product 4a are consistent with those reported in the prior art (Hu, J.; Tang, M.; Wang, J.; et al. Photocatalyzed Borylcyclopropanation of Alkenes with a (Diborylmethyl)Iodide Reagent[J]).

[0178] Example 28: Derivatization Experiment

[0179] ;

[0180] In an open flask, compound 3a (0.5 mmol, 1.0 equivalent) was dissolved in acetonitrile (2 mL) and methanol (2 mL). Then, an aqueous solution of cesium fluoride (containing 2.0 mmol cesium fluoride dissolved in 0.3 mL H 2 O) was added dropwise to the reaction solution. 2 O), and the mixture was stirred at room temperature for 5 minutes; then, L-(+)-tartaric acid (1.02 mmol, dissolved in 1 mL THF) was continuously added dropwise to the rapidly stirred transparent solution, and a white precipitate was precipitated. The reaction mixture was filtered to remove the white precipitate, and washed thoroughly with excess acetonitrile (5 mL), and then the filtrate was concentrated and recrystallized with n-hexane and diethyl ether to obtain the corresponding organic cesium trifluoroborate amorphous solid, which was further dried under vacuum for standby use.

[0181] In an argon-filled glove box, Pd(OAc) 2 (0.02 mmol, 10 mol%) and XPhos (0.04 mmol, 20 mol%), and then solid K 2 CO 3 (0.6 mmol, 3.0 equivalents), cesium trifluoroborate (0.24 mmol, 1.2 equivalents), bromobenzene (0.2 mmol, 1.0 equivalents), toluene (1.5 mL) and H 2 O (0.15 mL), sealed and taken out from the glove box. The reaction mixture was then reacted at 80 °C for 12 h. After the reaction was completed, the reaction mixture was cooled and concentrated, and the crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate = 60 / 1) to obtain the corresponding product 5a as a colorless oil with an isolated yield of 71%.

[0182] The NMR data of product 5a are: 1 H NMR (400 MHz, CD 2 Cl 2 ) d7.35 – 7.11 (m, 10H), 2.85 (m, 2H), 2.02 – 1.92 (m, 2H), 1.31 (d, J = 5.2 Hz, 1H), 1.28-1.25 (s, 6H), 1.25-1.23 (s, 6H), 1.13 (dd, J = 8.3, 3.6 Hz, 1H), 1.06 (dd, J = 6.2, 3.6 Hz, 1H). 13 C NMR (101 MHz, CD 2 Cl 2 ) d 146.4, 142.6, 129.4, 128.5, 128.2, 127.8,125.6, 125.1, 83.4, 36.2, 32.2, 27.9, 24.7, 24.4, 19.3. The NMR data of product 5a are consistent with those reported in the prior art (Ngo, DT; Jacob; Nagib, DA; et al. Cyclopropanationwith Non-Stabilized Carbenes via Ketyl Radicals[J]).

[0183] Example 29: Derivatization Experiment

[0184] ;

[0185] In an open flask, compound 3a (0.2 mmol, 1.0 equiv) was dissolved in THF (1 mL), and then sodium perborate (0.6 mmol, 3.0 equiv) was added, followed by H 2 O (1 mL), and the reaction solution was stirred at room temperature for 5 hours. 2 O (2 mL) to quench the reaction, and the mixture was extracted with ethyl acetate (3 × 5 mL). The organic layer was washed with anhydrous Na 2 SO 4 After drying and concentration in vacuo, the crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate = 40 / 1) to obtain the corresponding product 6a (CAS 2270-20-4) as a colorless oil with an isolated yield of 72%.

[0186] The NMR data of product 6a are: 1 H NMR (400 MHz, CDCl 3 ) d 9.78 (t, J= 2 Hz, 1H), 7.29(d, J = 9 Hz, 2H), 7.24 – 7.18 (m, 3H), 2.70 – 2.62 (m, 2H), 2.48 (m, 2H), 1.70(p, J = 4 Hz, 4H). 13 C NMR (101 MHz, CDCl 3 ) d 202.6, 141.9, 128.4, 128.4, 125.9,43.8, 35.6, 30.9, 21.7. The NMR data of product 6a are consistent with those reported in the prior art (Xiong, N.; Li, Y.; Zeng, R.; et al. Merging Photoinduced Iron-Catalyzed Decarboxylationwith Copper Catalysis for C–N and C–c Couplings[J]). Product 6a is widely used in the preparation of downstream chemical products such as 5-phenyl-n-pentanoic acid methyl ester, phenylpentanol, 4-phenyl-1-butyl bromide, and 5-(4-iodophenyl)pentanoic acid.

[0187] Example 30: Derivatization Experiment

[0188] ;

[0189] In an open flask, compound 3a (0.2 mmol, 1.0 equiv) was dissolved in THF (1 mL), and then sodium perborate (1.0 mmol, 5.0 equiv) was added, followed by H 2 O (1 mL), and the reaction solution was stirred at room temperature for 12 hours. 2 O (2 mL) to quench the reaction, and the mixture was extracted with ethyl acetate (3 × 5 mL). The organic layer was washed with anhydrous Na 2 SO 4 After drying and concentration in vacuo, the crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate = 40 / 1) to obtain the corresponding product 7a (CAS 529-34-0) as a colorless oil with an isolated yield of 63%.

[0190] The NMR data of product 7a are: 1 H NMR (400 MHz, CDCl 3 ) d 8.06 (d, J= 8 Hz, 1H), 7.50(m, 1H), 7.38 – 7.28 (m, 2H), 3.00 (t, J = 6 Hz, 2H), 2.71 – 2.67 (m, 2H), 2.20 – 2.15 (m, 2H). 13 C NMR (101 MHz, CDCl 3 ) d 198.4, 144.5, 133.4, 132.6, 128.8,127.2, 126.7, 39.2, 29.7, 23.3. The NMR data of product 7a are consistent with those reported in the prior art (Liu, J.; Hu, K.-F.; Qu, J.-P.; et al. Organopromoted Selectivity-Switchable Synthesis of Polyketones[J]). Product 7a is widely used in the preparation of downstream chemical products such as (S)-(-)-1,2,3,4-tetrahydro-1-naphthoic acid, 4-hydroxy-1-phenylbutan-1-one, 7-hydroxy-3,4-dihydro-2H-1-naphthalenone, 2,3-dihydro-1,4-naphthalenedione, and (S)-(+)-1,2,3,4-tetrahydro-1-naphthol.

[0191] Embodiment 31:

[0192] The experimental method is the same as in Example 1, except that the catalyst is fac-Ir(ppy) 3 (0.006 mmol, 2 mol%), [Ru(bpy) 3 ]Cl 2 (0.006 mmol, 2 mol%), Eosin Y (0.030 mmol, 10 mol%), [Mes-Acr] + [BF4] - (0.030 mmol, 10 mol%), 4-CzIPN (0.030 mmol, 10 mol%), Mn 2 (CO) 10 (0.030 mmol, 10mol%), Mn(CO) 5 Br (0.030 mmol, 10 mol%), Mn 2 (CO) 10 (0.015 mmol, 5 mol%). The yield data of the final prepared compound 3a are shown in Table 1.

[0193] Table 1

[0194]

[0195] a: Yield obtained by high performance gas chromatography-mass spectrometry analysis; b: Isolated yield.

[0196] Embodiment 32:

[0197] The experimental method is the same as in Example 1, except that the catalyst is Mn 2 (CO) 10 (0.030 mmol, 10 mol%), and the bases were lithium tert-butoxide (LiO t Bu), lithium tetramethylpiperidinium (LTMP), n-butyllithium ( n BuLi), the yield data of the finally prepared compound 3a are shown in Table 2.

[0198] Table 2

[0199]

[0200] a: The yield was obtained by high performance gas chromatography-mass spectrometry analysis.

[0201] Embodiment 33:

[0202] The experimental method is the same as in Example 1, except that the catalyst is Mn 2 (CO) 10 (0.030 mmol, 10 mol%), the base was lithium diisopropylamide (LDA), and the solvents were MeCN, DMF, THF, and DCM, respectively. The yield data of the finally prepared compound 3a are shown in Table 3.

[0203] Table 3

[0204]

[0205] a: The yield was obtained by high performance gas chromatography-mass spectrometry analysis.

[0206] Embodiment 34:

[0207] The experimental method is the same as in Example 1, except that no catalyst Mn is added. 2 (CO) 10 , the reaction progress was monitored and no compound 3a was obtained.

[0208] Embodiment 35:

[0209] The experimental method was the same as that in Example 1, except that no blue 440 nm LED light was used for illumination, and the reaction was carried out in the dark. The reaction progress was monitored, and compound 3a was not obtained.

[0210] The present invention provides a method and idea for preparing a geminal bis(boryl)cyclopropane compound. There are many methods and approaches to realize the technical solution. The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the protection scope of the present invention. All components not specified in this embodiment can be realized by existing technologies.

Claims

1. A method for preparing a geminal bis(boryl)cyclopropane compound, characterized in that: The olefin compound 1 and (diborylmethyl) iodide 2 undergo a halogen atom transfer radical addition reaction under the action of a catalyst and visible light, and then continue to undergo a deprotonation intramolecular cyclization reaction under the action of a base to obtain a geminal bis(boryl)cyclopropane compound 3; The structural formula of the olefin compound 1 is shown in Formula 1, the structural formula of the (diborylmethyl)iodide 2 is shown in Formula 2, and the structural formula of the geminal bis(boryl)cyclopropane-containing compound 3 is shown in Formula 3: in, R is selected from substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, or substituted or unsubstituted C3-C6 cycloalkenyl; wherein the substitution is selected from substitution by any number of identical or different substituents; the substituent is halogen, C1-C4 alkoxycarbonyl or C1-C4 alkoxy; or, R is selected from n is an integer selected from 1 to 3; R1 is selected from substituted or unsubstituted naphthyl, substituted or unsubstituted phenyl, substituted or unsubstituted indolyl, substituted or unsubstituted azafluorenyl; m is an integer selected from 1 to 4; R2 is selected from substituted or unsubstituted phenyl, substituted or unsubstituted C3-C6 cycloalkyl, z is an integer selected from 1 to 3; R3, R4, and R5 are independently selected from substituted or unsubstituted C1-C4 alkyl, or substituted or unsubstituted phenyl; Wherein, the substitution is selected from substitution by any number of identical or different substituents; the substituent is halogen, C1-C4 alkyl substituted with 1 to 3 halogens, or C1-C4 alkyl; The catalyst is dimanganese decacarbonyl; The base is lithium diisopropylamide or lithium tetramethylpiperidinium; The wavelength of the visible light is 440nm.

2. The preparation method according to claim 1, characterized in that: R is selected from substituted or unsubstituted C2-C5 alkyl, substituted or unsubstituted C6 cycloalkyl, or substituted or unsubstituted C6 cycloalkenyl; wherein the substitution is selected from substitution by any number of identical or different substituents; the substituent is halogen, C1-C2 alkoxycarbonyl or C1-C2 alkoxy; or, R is selected from n is an integer selected from 1 to 3; R1 is selected from substituted or unsubstituted naphthyl, substituted or unsubstituted phenyl, substituted or unsubstituted indolyl, substituted or unsubstituted azafluorenyl; m is an integer selected from 1 to 4; R2 is selected from substituted or unsubstituted phenyl, substituted or unsubstituted C6 cycloalkyl, z is an integer selected from 1 to 2; R3, R4, R5 are independently selected from C1-C2 alkyl or phenyl; Wherein, the substitution is selected from substitution by any number of identical or different substituents; the substituent is halogen, C1-C2 alkyl or C1-C3 alkyl substituted with 1 to 3 halogens.

3. The preparation method according to claim 1, characterized in that: R is selected from substituted or unsubstituted ethyl, substituted or unsubstituted propyl, isobutyl, tert-butyl, pentyl, cyclohexyl or cyclohexenyl; wherein the substitution is selected from substitution by any number of identical or different substituents; the substituent is chlorine, methoxycarbonyl or methoxy; or, R is selected from n is an integer selected from 1 to 3; R1 is selected from naphthyl, phenyl, substituted or unsubstituted indolyl, azafluorenyl; m is an integer selected from 1 to 4; R2 is selected from substituted or unsubstituted phenyl, substituted cyclohexyl, z is selected from 2; R3, R4, R5 are independently selected from methyl or phenyl; Wherein, the substitution is selected from substitution by any number of identical or different substituents; the substituent is fluorine, chlorine, bromine, iodine, trifluoromethyl, methyl or isopropyl.

4. The preparation method according to claim 1, characterized in that: The molar ratio of the olefin compound 1 to the (diboronmethyl) iodide 2 is (1.0-1.5):1.2; the molar ratio of the olefin compound 1 to the catalyst is 1.0:0.02-0.

15.

5. The preparation method according to claim 1, characterized in that: The reaction temperature of the halogen atom transfer free radical addition reaction is 25° C. to 40° C.; the halogen atom transfer free radical addition reaction is carried out under the protection of an inert gas.

6. The preparation method according to claim 1, characterized in that: The solvent used in the halogen atom transfer free radical addition reaction is n-hexane, dichloromethane or tetrahydrofuran.

7. The preparation method according to claim 1, characterized in that: The molar ratio of the olefin compound 1 to the base is 1.0:(1.0-1.5).

8. The preparation method according to claim 1, characterized in that: The reaction temperature of the deprotonated intramolecular cyclization reaction is -20°C to 10°C; the deprotonated intramolecular cyclization reaction is carried out under the protection of an inert gas.

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