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A b(3)/b(3,6)-o-carborarylation method of a compound

A compound, carborane technology, applied in the field of B/B-o-carborylation of compounds, can solve the problem of insufficient evaluation of method universality, lack of evaluation of synthetic chemistry applicability, narrow scope of substrate application, etc. problem, achieve good solubility and functional group compatibility, and avoid environmental pollution

Active Publication Date: 2021-05-14
NANJING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

(3) The scope of substrate application is relatively narrow, and at least one assessment of the applicability of a broad synthetic chemistry is relatively lacking
Although there are already some B(3) / B(4)—C(sp 2 ) coupling, but the generalizability of these methods has not been fully evaluated

Method used

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  • A b(3)/b(3,6)-o-carborarylation method of a compound
  • A b(3)/b(3,6)-o-carborarylation method of a compound
  • A b(3)/b(3,6)-o-carborarylation method of a compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] The screening of embodiment 1 reaction conditions

[0040] According to the conditions in Table 1, compound 40 (1-[(1E)-2-(2,4,6-trimethylphenylethenyl)]-1,2-dicarbadodecaborane, 58.2 mg, 0.2 mmol), active amide (a, b , c, d or e) (0.44mmol), rhodium catalyst (0.01mmol) was added to a dried 10mL Schlenk tube, pumped three times with argon. When toluene (1.0 mL) was added, the tube was closed. After 24 hours the tube was cooled to room temperature and filtered through 2 cm of celite with an ethyl acetate rinse. Celite was rinsed with DCM (2 x 5 mL). The collected organic solvent was spin-dried and separated by preparative TLC (PTLC) to obtain mono-substitution (mono) and di-substitution (di).

[0041]

[0042] Mes stands for

[0043] Table 1

[0044]

[0045] The results show that compound 40 and active amide a are under standard conditions (5mol%, [Rh(cod)Cl] 2 The product was obtained in 93% isolated yield (mono-:di-=11:82, Example 1) in toluene, stirring...

Embodiment 2

[0047] Preparation of active amides with N-acyl-imide groups

[0048] n=2 or 3:

[0049] The following example can be used to prepare

[0050] Option A:

[0051]

[0052] Option B:

[0053]

[0054] Option C:

[0055]

[0056] Fragments of the compound moiety having an N-acyl-imide group are selected from:

[0057]

[0058]

[0059] (2) Preparation of mono- / di-carborarylated compounds

[0060] With reference to the method of Example 1, the optimal reaction conditions were selected, and the active amide obtained in step (1) was cross-coupled with compound 40 to investigate the carborylation (B (3) apex) reaction under optimal conditions practicality.

[0061] The results show that N-acyl-glutarimides with electron-donating groups (EDG) or electron-withdrawing groups (EWG) at the para position react smoothly (groups 2-14), while compounds with EWG have better The yield of (group 5-18). Methoxy (group 2), 2,4,6-trimethylphenyl (group 3), alkenyl (group 4)...

Embodiment 5

[0199] Example 5 Further transformation of B(3) / B(3,6)-o-carborarylate

[0200] (1) Taking compound 1 as an example, carry out gram-level synthesis

[0201]

[0202] Add compound 40 (1000.0mg, 3.44mmol), active amide a (1650.0mg, 7.57mmol), [Rh(cod)Cl] 2 (96.3 mg, 0.17 mmol). Pump three times to change to Ar atmosphere, and add toluene 17mL. 1-mono (185.6 mg, 0.52 mmol, 15%) and 1-di (1141.9 mg, 2.61 mmol, 76%) were obtained by column chromatography.

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Abstract

The invention discloses a B(3) / B(3,6)-o-carborylation method of a compound, derivatizing the compound into an active amide with an N-acyl-imide group. Under the catalysis of Rh catalyst, cross-coupling with o-carborane with imine group on the cage carbon. The method of the present invention can realize the carborylation modification of functional compounds such as pharmaceutical active substances and fluorescent molecules, and can also perform functional grouping on the B(3) / B(3,6) position of o-carborane. Compared with the traditional coupling method, the present invention realizes direct B-H activation and functionalization, and overcomes environmental pollution, dangerous reaction conditions and yield loss in multi-step reactions caused by B(3) pre-activation in the prior art And other disadvantages, the reaction has better solubility and functional group compatibility, and has better industrial application prospects.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, and in particular relates to a B(3) / B(3,6)-o-carborarylation method of a compound. Background technique [0002] Carborane is a class of polyhedral carbon-boron molecular clusters, and the twelve-vertex icosahedral double-carbon closed-carborane (closo–C 2 B 10 h 12 , hereinafter will be abbreviated as "carborane"), there are three isomers, ortho carborane is due to its three-dimensional aromaticity, large steric hindrance, multiple directional B—H and C—H bonds and Special properties such as non-classical interactions are widely used in luminescent materials, metal organic frameworks, nanoscale materials, electronic storage materials, liquid crystals, catalysis, etc., and can be used as good "model molecules" in physical organic chemistry research. O-carboranes have a very high boron content and have potential applications in boron neutron capture therapy. Hosmane has developed a water-solu...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F5/05
CPCC07F5/05
Inventor 燕红芦昌盛李春晓
Owner NANJING UNIV