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Chiral ferrocene diphosphine ligand and preparation method thereof

A technology of dichlorination and compound is applied in the field of chiral ferrocene bisphosphine ligand and its preparation, which can solve the problems such as being difficult to obtain, and achieve the effect of expanding the scope of application

Inactive Publication Date: 2014-05-21
FOURTH MILITARY MEDICAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the disadvantage of this method is that many aryl (alkyl) phosphine dichlorides are not easily available, and the substituents on the phosphorus atom can only be changed to a limited extent.

Method used

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  • Chiral ferrocene diphosphine ligand and preparation method thereof
  • Chiral ferrocene diphosphine ligand and preparation method thereof
  • Chiral ferrocene diphosphine ligand and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] [( R C , R C ),( S Fc , S Fc ),( S P , S P )]-1,1′-bis[2-(1- N , N -Dimethylaminoethyl)-1-ferrocenyl] the preparation of phenylphosphinoferrocene (Trifer)

[0043] Towards( R )-Ugi′s amine (2.57 g, 10 mmol) was injected with 20 mL of dry tert-butyl methyl ether (TBME), placed in an ice-water bath, and 1.3 M of t -BuLi (8.5 mL, 11.05 mmol), after the dropwise addition, the reaction was raised to room temperature for 1.5 hours; the reaction solution was placed in a low-temperature reactor at -78°C, and PCl dissolved in 5 mL TBME was slowly added dropwise below -78°C 3 (1 mL, 11.46 mmol), after the dropwise addition, the reaction was raised to room temperature for 1.5 hours to generate dichloro 2; Place the reaction below -78°C again, slowly add the suspension of phenyllithium [bromobenzene (1.75 g, 11.1 mmol) at -40°C at 1.6 M n -BuLi (7.6 mL, 12.16mmol) was prepared by lithiation for 2 hours] After the addition, the reaction was raised to room temperatur...

Embodiment 2

[0045] [( R C , R C ),( S Fc , S Fc ),( S P , S P )]-1,1′-bis[2-(1- N , N -Dimethylaminoethyl)-1-ferrocenyl]cyclohexylphosphinoferrocene (Cy-Trifer) preparation

[0046] The preparation method is the same as that of Example 1, and the suspension of phenyllithium is replaced with a THF solution (11 mL, 11 mmol) of 1.0 MCyMgBr to obtain 2.08 g of the product Cy-Trifer, with a yield of 45%; m.p.: 182.5-185.5oC; [ α] = -302.9 (c = 0.25, CH 2 Cl 2 ); 1 H NMR (400 Hz, CDCl 3 ) δ4.67 (s, 2H), 4.50 (d, J = 9.0 Hz, 4H), 4.31 (s, 2H), 4.24 (s, 2H), 4.10-3.99 (m, 4H), 3.93 (s, 10H), 3.69 (s, 2H), 2.42-2.27 (m, 2H), 2.13 (s, 12H), 2.03-1.92 (m, 2H), 1.86-1.57 (m, 11H), 1.36-1.16 (m, 6H), 1.27 (d, J = 6.6 Hz, 7H); 31 P NMR (162 Hz, CDCl 3 ) δ -26.25 (s); 13 C NMR (101 Hz, CDCl 3 ) δ96.35 (d, J = 22.9 Hz), 79.61 (d, J = 8.1 Hz), 78.92 (d, J = 16.1 Hz), 76.46 (d, J = 33.2 Hz), 72.00 (d, J = 5.5 Hz), 71.76 (d, J = 4.9 Hz), 70.97 (d, J = 7.5 Hz), 69.52 ...

Embodiment 3

[0048] ( R C , S Fc , S P )-1-[2-(1- N , N Preparation of -Dimethylaminoethyl)-1-ferrocenyl]phenylphosphino-1'-dicyclohexylphosphinoferrocene (ChenPhos)

[0049] monochloride 3 The preparation is the same as that in Example 1. The reaction solution is placed in a low-temperature reactor at -78°C, and 1-bromo-1'-lithium ferrocene [below -20°C, 1,1'-dibromobis Ferrocene (3.76 g, 11 mmol) and 1.6 M n -BuLi (7.6 mL, 12.16mmol) was prepared by reacting in THF for 2 hours], after the addition, the reaction was raised to room temperature and reacted for 1.5 hours to generate an intermediate 6 , place the reaction solution below -60°C, add dropwise 1.3 M t -BuLi (8.5 mL, 11.05mmol), reacted at -60°C for 2 hours after the dropwise addition, slowly added Cy 2 A solution of PCl (2.7 mL, 12.2 mmol) in 5 mL of dry TBME was added dropwise and then raised to room temperature to react overnight. The reaction was quenched by adding saturated ammonium chloride solution, the organic ...

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Abstract

The invention provides a chiral ferrocene diphosphine ligand and a preparation method thereof, and discloses a compound as shown in a general structural formula (I), wherein R is selected from C1-C25 alkyl, aryl or substituted aryl, hetero-aryl and cycloalkyl; R' is selected from C1-C25 alkyl, aryl or substituted aryl, hetero-aryl and cycloalkyl. In the chiral ferrocene diphosphine ligand disclosed by the invention, various substituent groups can be conveniently introduced above phosphorus atoms, and electrons and three-dimensional properties of the phosphine ligand are easy to be changed, so that the application range of the phosphine ligand in different catalytic reactions can be farthest widened.

Description

technical field [0001] The invention relates to a chiral ferrocene bisphosphine ligand and a preparation method thereof, belonging to the technical field of organic synthesis. Background technique [0002] P -Chiral ferrocene ligands Trifer and ChenPhos are very important chiral ferrocene phosphine ligands in the field of asymmetric catalysis. They address the asymmetric hydrogenation of several classes of challenging substrates or some substrates cannot be hydrogenated with high selectivity and efficiency. The reason for the high stereoselectivity and high activity of these two types of ligands is that the dimethylamine group in the ligands produces a second interaction through electrostatic or hydrogen bonding. The asymmetric hydrogenation of substituted cinnamic acids and cinnamyl alcohols that can generate a second interaction with the ligands has achieved high stereoselectivity and catalytic activity. Due to their excellent catalytic performance, Trifer and ChenPhos ...

Claims

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Application Information

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IPC IPC(8): C07F17/02
Inventor 陈卫平张生勇姚伟
Owner FOURTH MILITARY MEDICAL UNIVERSITY
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