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Method for synthesizing C2-symmetrical chiral ferrocenyl phosphine compound

A technology for chiral ferrocene and phosphine compounds, applied in chemical instruments and methods, metallocene, organic chemistry, etc., can solve the problems of cumbersome steps, unfavorable for industrial scale-up, low yield, etc. Selective, few-step effect

Active Publication Date: 2016-10-26
PUYANG HUICHENG ELECTRONICS MATERIAL
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The steps of this route are cumbersome, and the yield of the step of introducing chlorophosphine after dilithiation is low, which is not conducive to industrial scale-up

Method used

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  • Method for synthesizing C2-symmetrical chiral ferrocenyl phosphine compound
  • Method for synthesizing C2-symmetrical chiral ferrocenyl phosphine compound
  • Method for synthesizing C2-symmetrical chiral ferrocenyl phosphine compound

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Experimental program
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Effect test

Embodiment 1

[0021] Embodiment 1 (1) 1, the synthesis of 1 '-bis [(R)-(dimethylamino) (phenyl) methyl] ferrocene

[0022] Add 1L of 1,2-dichloroethane, N,N-dimethylbenzamide (1mol, 149g) and dimethyl sulfate (1mol, 126g) to the dry reactor successively, react at 50°C for 3 hours, Then add ferrocene (0.5mol, 93g) and (R)-3,3'-bis(4-nitrophenyl)-1,1'-binaphthyl phosphonate (0.005mol, 3g), in React at 10°C for 12 hours, then dropwise add 1M zinc borohydride solution in tetrahydrofuran (1mol, 1L), after reacting at 0°C for 2 hours, slowly add 1L of 10% by mass sodium hydroxide aqueous solution dropwise to the system, and then separate the liquids , the organic layer was dried with anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a yellow solid, which was recrystallized from n-hexane to obtain 1,1'-bis[(R)-(dimethylamino)(phenyl)methyl ] Ferrocene 210g, productive rate 93%, e.e. value 99.3%. 1 H NMR (400MHz, CDCl 3 ),δ:7.42-7.26(m,10H)...

Embodiment 2

[0025] Embodiment 2 (1) 1, the synthesis of 1 '-bis [(R)-(dimethylamino) (phenyl) methyl] ferrocene

[0026] Add 1L 1,2-dichloroethane, N,N-dimethylbenzamide (1.25mol, 186g) and dimethyl sulfate (1.25mol, 157g) to the dry reactor successively, and react at 80°C for 2 hours, then added ferrocene (0.5mol, 93g) and (R)-3,3'-bis(4-nitrophenyl)-1,1'-binaphthyl phosphonate (0.025mol, 14.7g ), react at 30°C for 10 hours, and finally add 1M zinc borohydride solution in tetrahydrofuran (1.5mol, 1.5L) dropwise, and after reacting at 30°C for 1 hour, slowly add 1L of 10% by mass sodium hydroxide dropwise to the system aqueous solution, and then separated, the organic layer was dried with anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a yellow solid, which was recrystallized from n-hexane to obtain 1,1'-bis[(R)-(dimethylamino)( Phenyl)methyl]ferrocene 215g, yield 95%, e.e. value 99.4%.

[0027] (2) (S,S)-(-)-2,2'-bis[(R)-(N,N-di...

Embodiment 3

[0029] Embodiment 3 (1) 1, the synthesis of 1 '-bis [(R)-(dimethylamino) (phenyl) methyl] ferrocene

[0030] Add 1L 1,2-dichloroethane, N,N-dimethylbenzamide (1.1mol, 164g) and dimethyl sulfate (1.1mol, 139g) to the dry reactor successively, and react at 70°C for 3 hours, then added ferrocene (0.5mol, 93g) and (R)-3,3'-bis(4-nitrophenyl)-1,1'-binaphthyl phosphonate (0.01mol, 6g) , reacted at 25°C for 12 hours, and finally added dropwise 1M tetrahydrofuran solution of zinc borohydride (1.2mol, 1.2L). After reacting at 25°C for 2 hours, slowly added 1L of 10% by mass aqueous sodium hydroxide solution dropwise to the system , then separated, the organic layer was dried with anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a yellow solid, which was recrystallized from n-hexane to obtain 1,1'-bis[(R)-(dimethylamino)(benzene Base) methyl] ferrocene 215g, productive rate 95%, e.e. value 99.4%.

[0031] (2) (S,S)-(-)-2,2'-bis[...

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Abstract

The invention discloses a method for synthesizing a C2-symmetrical chiral ferrocenyl phosphine compound and belongs to the field of organic synthesis. The method comprises the following implementation steps: (1) subjecting ferrocene, which serves as a starting raw material, to a reaction with a complex of N,N-dimethyl benzamide and dimethyl sulfate in the presence of a chiral catalyst, and then, carrying out reduction by zinc borohydride so as to obtain 1,1'-bis[(R)-(dimethylamido)(phenyl)methyl]ferrocene; and (2) subjecting 1,1'-bis[(R)-(dimethylamido)(phenyl)methyl]ferrocene to a reaction with n-butyl lithium, then, subjecting a reaction product to an action with cerium trichloride, and then, carrying out a reaction with R2PCl, thereby obtaining the C2-symmetrical chiral ferrocenyl phosphine compound. Compared with the prior art, the method has the advantages of simple steps and high yield, thereby being more applicable to industrial production. After the prepared C2-symmetrical chiral ferrocenyl phosphine compound is subjected to complexation with metal, an asymmetric organic reaction can be catalyzed, so that the C2-symmetrical chiral ferrocenyl phosphine compound is applied to the field of synthesis of pharmaceutical intermediates.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and relates to a synthesis method of a class of organic phosphine compounds, in particular to a synthesis method of a C2-symmetrical chiral ferrocene phosphine compound. Background technique [0002] Chiral ferrocene phosphine compounds containing C2-symmetry are an important class of ligands in ferrocene chiral derivatives. After complexing with metals, these compounds can catalyze the asymmetric hydrogenation of alkenes, vinyl bromide and Grignard reagents. It has achieved good results in asymmetric coupling and optically active amino acid synthesis, and has been widely used in the field of pharmaceutical intermediate synthesis. [0003] At present, the synthesis of such C2-symmetric chiral ferrocene phosphine compounds mainly involves the Friedel-Crafts reaction of ferrocene and benzoyl chloride to obtain 1,1'-bis(benzoyl)ferrocene, and then through CBS Reduction to obtain chiral diol, and th...

Claims

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Application Information

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IPC IPC(8): C07F17/02C07F19/00
CPCC07F17/02
Inventor 陈辉杨瑞娜杨振强孙敏青王从洋屈凤波
Owner PUYANG HUICHENG ELECTRONICS MATERIAL
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