Iridium complex containing carbonboryl benzimidazole structure and preparation method and application thereof

A technology containing carboryl benzimidazole and carboryl benzimidazole, which is applied in the field of semi-sandwich iridium complexes and its preparation, can solve the problems of wasting reagents, cumbersome steps, environmental damage, etc., and achieve high stability , The synthesis process is simple, and the effect of general applicability is good

Active Publication Date: 2019-08-09
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The traditional preparation method of chiral alcohols is mainly obtained from racemic aromatic alcohols through mult

Method used

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  • Iridium complex containing carbonboryl benzimidazole structure and preparation method and application thereof
  • Iridium complex containing carbonboryl benzimidazole structure and preparation method and application thereof
  • Iridium complex containing carbonboryl benzimidazole structure and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Synthesis of semi-sandwich iridium complex Ir containing ortho carboryl benzimidazole structure:

[0031]

[0032] At -78°C, n-BuLi (1.6M) in n-hexane (1.00 mL, 1.6 mmol) was slowly added dropwise to the o-C 2 B 10 h 10 (92.0mg, 0.64mmol) in tetrahydrofuran solution, stirred at this temperature for 30 minutes, slowly rose to room temperature and continued to react for 1 hour, then added bromobenzimidazole (126.7mg, 0.64mmol), and continued to react at room temperature for 6 Hour. Then the binuclear iridium compound [Cp*IrCl 2 ] 2 (256.0 mg, 0.32 mmol) was added to the reaction system for an additional 3 hours. After the reaction was finished, stand and filter, and dry the solvent under reduced pressure, and the obtained crude product was separated by column chromatography (petroleum ether / tetrahydrofuran=6:1) to obtain the red target product iridium (III) complex Ir (322.4 mg, yield rate 81%).

[0033] 1 H NMR (400MHz, CDCl 3 ,25℃):δ=8.03(brs,1H),7.89(d,J=7....

Embodiment 2

[0037] Iridium(III) complexes catalyze the asymmetric reduction of aryl ketones:

[0038]

[0039] The iridium complex prepared in Example 1 was used as a catalyst to catalyze the asymmetric reduction reaction of aryl ketone: in acetophenone (10mmol, 1.20g), a trivalent iridium complex (0.01mmol, 13.0g) containing an ortho carborane structure was added mg) in ethanol solution, under normal pressure, hydrogen gas was introduced as a reducing agent to react, the reaction temperature was 80°C, and the reaction time was 120 minutes. chiral alcohol compound C 8 h 10 O (yield 91%), ee>99%, elemental analysis: C 78.65, H 8.25 (theoretical); C 78.59, H 8.22 (actual).

Embodiment 3

[0041] Iridium(III) complexes catalyze the asymmetric reduction of aryl ketones:

[0042]

[0043] The iridium complex prepared in Example 1 is used as a catalyst to catalyze the asymmetric reduction reaction of aryl ketone: in 4-methoxyacetophenone (10mmol, 1.50g), add a trivalent iridium complex containing an ortho carborane structure (0.01mmol, 13.0mg) in ethanol solution, and pass into hydrogen as a reducing agent to react, the reaction temperature is 80°C, and the reaction time is 60 minutes. After the end, the concentrated reaction solution is directly separated by silica gel column chromatography, and dried until the mass remains unchanged , to obtain the corresponding chiral alcohol compound C 9 h 12 o 2 (96% yield), ee>99%, elemental analysis: C 71.03, H 7.95 (theoretical); C 71.00, H 7.81 (actual).

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Abstract

The invention relates to an iridium complex containing a carbonboryl benzimidazole structure and a preparation method and application thereof. The preparation method of the iridium complex comprises the following steps that 1, an n-BuLi solution is added into an carborane solution for a reaction at the room temperature for 30-60 minutes; 2, bromobenzimidazole is added for a reaction at the room temperature for 6-8 hours; 3, [Cp*IrCl2]2 is added for a reaction at the room temperature for 3-5 hours, and post-treatment is carried out to obtain the iridium complex; the iridium complex is used forcatalyzing asymmetric reduction of aromatic ketones to prepare chiral alcohol compounds. Compared with the prior art, the iridium complex adopts the dual-core iridium compound [Cp*IrCl2]2 as a raw material which reacts with n-BuLi and ortho-carbonboryl benzimidazole to obtain the trivalent iridium complex containing the ortho-carbonboryl benzimidazole structure. The iridium complex has stable physical and chemical properties and thermal stability, a synthesis process is simple and environmentally friendly, and the iridium complex catalyzes an asymmetric reduction reaction of aromatic ketones to synthesize chiral alcohol compounds under mild conditions and has excellent catalytic activity and enantioselectivity and a high yield.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry, and relates to a semi-sandwich iridium complex containing an ortho-carboryl benzimidazole structure and a preparation method and application thereof. Background technique [0002] Chiral aromatic alcohols are a class of high-tech, high-value-added products. As a class of important organic synthesis intermediates, they have been widely used in the fields of medicine and pesticides. Therefore, how to efficiently synthesize chiral alcohols has always been one of the focuses in the field of chemistry. The traditional preparation method of chiral alcohols is mainly obtained from racemized aromatic alcohols through multi-stage resolution, which not only has cumbersome steps, but also wastes reagents and causes great damage to the environment. In recent years, in order to meet the requirements of green synthesis, researchers have developed a variety of preparation methods for chiral alcohol...

Claims

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Application Information

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IPC IPC(8): C07F17/00C07B53/00B01J31/22C07C29/145C07C33/22C07C41/26C07C43/23C07C201/12C07C205/19C07C33/46
CPCB01J31/2295B01J2231/643B01J2531/827C07B53/00C07B2200/07C07C29/145C07C41/26C07C201/12C07F17/00C07C33/22C07C43/23C07C205/19C07C33/46
Inventor 姚子健樊晓楠高永红邓维
Owner SHANGHAI INST OF TECH
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