Half-sandwich rhodium complex with ortho-position carborane benzoxazole structure as well as preparation method and application of half-sandwich rhodium complex

A carboryl benzoxazole and rhodium complex technology, which is applied in the preparation of hydroxyl compounds, organic compounds, organic compound/hydride/coordination complex catalysts, etc., can solve the problem of poor yield and selectivity, Low catalytic activity and other problems, to achieve high yield, high catalytic efficiency and high stability

Active Publication Date: 2021-03-23
SHANGHAI APPLIED TECHNOLOGIES COLLEGE
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  • Abstract
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  • Application Information

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Problems solved by technology

[0003] The purpose of the present invention is to provide a semi-sandwich rhodium complex of ortho-carborane benzoxazole structure and its preparation method and application, which is used to solve the problem of low catalytic activity, low yield and low production rate in the existing chiral alcohol catalytic synthesis method. less selective problem

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  • Half-sandwich rhodium complex with ortho-position carborane benzoxazole structure as well as preparation method and application of half-sandwich rhodium complex
  • Half-sandwich rhodium complex with ortho-position carborane benzoxazole structure as well as preparation method and application of half-sandwich rhodium complex
  • Half-sandwich rhodium complex with ortho-position carborane benzoxazole structure as well as preparation method and application of half-sandwich rhodium complex

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preparation example Construction

[0030] The preparation method of above-mentioned semi-sandwich rhodium complex comprises the following steps:

[0031] 1) At -85 to -70°C, add n-BuLi's n-hexane solution dropwise to the ortho carborane o-C 2 B 10 h 12 THF solution, and continue to stir for 20-40min, then the solution is slowly warmed up to room temperature, and then continue to react for 30-60min;

[0032] 2) Add bromobenzoxazole and react at room temperature for 6-8h;

[0033] 3) Add [Cp*RhCl 2 ] 2 , and react at room temperature for 3-5h, and then undergo static filtration, decompression to dry the solvent, and column chromatography to obtain the red target product, a half-sandwich rhodium complex.

[0034] Among them, n-BuLi, o-carborane, bromobenzoxazole and [Cp*RhCl 2 ] 2 The molar ratio is (2.2-3.0):1:1:0.5; during the column chromatography separation process, the eluent used is a mixed reagent composed of petroleum ether and tetrahydrofuran in a volume ratio of (5-10):1.

[0035] The above-menti...

Embodiment 1

[0039] This embodiment is used to synthesize the semi-sandwich rhodium complex [Rh] containing an ortho carboryl benzoxazole structure, and the specific preparation method includes the following steps:

[0040]

[0041] I) Slowly add n-BuLi (1.6M) n-hexane solution (1.00mL, 1.6mmol n-BuLi) dropwise to the ortho carborane o-C at -78°C 2 B 10 h 10 (92.0mg, 0.64mmol) in tetrahydrofuran solution, and kept stirring at this temperature for 30min;

[0042] II) The product solution obtained in step I) was slowly warmed to room temperature, and continued to stir for 1 h, then added bromobenzoxazole (126.7 mg, 0.64 mmol), and reacted at room temperature for 6 h;

[0043] III) the binuclear rhodium compound [Cp*RhCl 2 ] 2 (256.0mg, 0.32mmol) was added into the product solution obtained in step II), and stirred for 3h; / ethyl acetate=6:1), the red target product rhodium (III) complex [Rh] (245.6 mg, yield 72%) was obtained.

[0044] Product characterization results are as follows...

Embodiment 2

[0052] In this embodiment, the rhodium (III) complex [Rh] in Example 1 is used as a catalyst to catalyze the asymmetric reduction reaction of aliphatic ketones, and the specific process is as follows:

[0053]

[0054] Add the ethanol solution of the rhodium (III) complex [Rh] (0.01mmol, 5.3mg) to the butanone solution (10mmol, 0.72g), and pass hydrogen gas under normal pressure as a reducing agent to react, and control the reaction temperature The temperature is 80°C, and the reaction time is 120 minutes; after the reaction is completed, the product mixture is concentrated, separated by silica gel column chromatography, and dried to constant weight to obtain the target product chiral alcohol compound C 4 h 10 O (94% yield), ee>99%.

[0055] Product characterization results are as follows:

[0056] Elemental analysis theoretical value: C 64.82, H 13.60; experimental value: C 64.89, H 13.62, the characterization results show that the chiral alcohol compound C was successfu...

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Abstract

The invention relates to a half-sandwich rhodium complex with an ortho-position carborane benzoxazole structure as well as a preparation method and application of the half-sandwich rhodium complex. The structural formula of the rhodium complex is shown in the specification. The preparation method comprises the following steps: firstly, adding an n-BuLi solution into an ortho-position carborane solution, and then reacting for 30-60 minutes at room temperature; adding bromo-benzoxazole, and carrying out a reaction for 6-8 h at a room temperature; and adding [Cp * RhCl2] 2, reacting at room temperature for 3-5 hours, and carrying out post-treatment to obtain the rhodium complex. The rhodium complex can be used as a catalyst to catalyze the asymmetric reduction reaction of aliphatic chiral alcohol compounds synthesized from aliphatic ketones. Compared with the prior art, the rhodium complex disclosed by the invention has the advantages of simple preparation method, stable physicochemical properties, high catalytic activity for asymmetric reduction reaction of aliphatic ketone, mild reaction conditions and the like.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry, and relates to a semi-sandwich rhodium complex with an ortho carborane benzoxazole structure and a preparation method and application thereof. Background technique [0002] Chiral alcohols are a class of high-tech, high value-added products, and as an important intermediate in organic synthesis, they are widely used in the fields of medicine and pesticides. The traditional preparation method of chiral alcohol is obtained from racemic alcohol through multi-stage resolution. This method not only has cumbersome steps, but also consumes a lot of reagents and produces more waste liquid, which has a great impact on the environment. In recent years, in order to meet the requirements of green chemistry, a variety of preparation methods of chiral alcohols have been developed. Among these methods, the preparation method of chiral alcohols synthesized by using catalysts to catalyze the asymmetr...

Claims

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Application Information

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IPC IPC(8): C07F15/00C07F17/02B01J31/22C07B53/00C07C29/145C07C31/12C07C31/125C07C31/36C07C41/26C07C43/13
CPCC07F15/0073C07F17/02B01J31/2295C07B53/00C07C29/145C07C41/26C07B2200/07B01J2531/822B01J2231/643C07C31/12C07C31/125C07C31/36C07C43/13Y02P20/584
Inventor 姚子健零春关艾琳
Owner SHANGHAI APPLIED TECHNOLOGIES COLLEGE
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