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Phosphoramidite type diphosphine ligand, preparation method and application thereof

A technology of bidentate phosphine ligands and phosphonamidites, which is applied in the field of phosphonamidite bidentate phosphine ligands and their preparation, and can solve problems such as difficulties in the synthesis of bisphosphine ligands

Inactive Publication Date: 2008-12-31
WUHAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although a considerable number of chiral bisphosphine ligands with excellent properties have been reported, the synthesis of many bisphosphine ligands is relatively difficult.

Method used

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  • Phosphoramidite type diphosphine ligand, preparation method and application thereof
  • Phosphoramidite type diphosphine ligand, preparation method and application thereof
  • Phosphoramidite type diphosphine ligand, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Preparation of 4,4',6,6'-tetrakis(trifluoromethyl)-N,N'-bis(diisopropylphosphino)-biphenyl-2,2'-diamine (R)-2a

[0026] Add 0.5 g of (R)-4,4',6,6'-tetrakis(trifluoromethyl)biphenyl-2,2'-diamine into a 50 mL Schlenk bottle, and add anhydrous and oxygen-free tetrahydrofuran under the protection of Ar gas 7.5 mL, at -40°C, add 2M n-BuLi (1.1 ml, 2.0 eq), react for 20-30 minutes, add diisopropylphosphine chloride (2.2 eq) with a syringe, and continue the reaction for 1 hour, naturally After warming up to room temperature and reacting for 24 hours, the solvent was spin-dried and subjected to basic alumina column chromatography (petroleum ether was used as eluent) to obtain 0.33 g of the product with a yield of 53.1%.

[0027] (R)-2a: mp 63-66°C; [α] 25 D =-188.8 (c 0.91, CHCl 3 ).IR (KBr) v 3371, 2967, 2938, 2897, 2870, 1620, 1584, 1508, 1441, 1398, 1386, 1286, 1265, 1170, 1138cm -1 ; 1 H NMR (CDCl 3 , TMS, 300MHz) δ0.78-0.99(m, 24H), 1.56-1.65(m, 4H), 3.68(d, J=8.7Hz,...

Embodiment 2

[0029] Preparation of 4,4',6,6'-tetrakis(trifluoromethyl)-N,N'-bis(diisopropylphosphino)-biphenyl-2,2'-diamine (R)-2a

[0030] Add 0.5 g of (R)-4,4',6,6'-tetrakis(trifluoromethyl)biphenyl-2,2'-diamine into a 50 mL Schlenk bottle, and add anhydrous and oxygen-free tetrahydrofuran under the protection of Ar gas Add 2M n-BuLi (1.1ml, 2.0eq) to 7.5mL at -20°C, react for 20-30 minutes, then add diisopropylsulfuric acid chloride (2.2eq) with a syringe, and continue to react for 1h. After warming up to room temperature and reacting for 24 hours, the solvent was spin-dried and subjected to basic alumina column chromatography (petroleum ether was used as eluent) to obtain 0.31 g of the product with a yield of 50.0%.

Embodiment 3

[0032] Preparation of 4,4',6,6'-tetrakis(trifluoromethyl)-N,N'-bis(diisopropylphosphino)-biphenyl-2,2'-diamine (R)-2a

[0033] Add 0.5 g of (R)-4,4',6,6'-tetrakis(trifluoromethyl)biphenyl-2,2'-diamine into a 50 mL Schlenk bottle, and add anhydrous and oxygen-free tetrahydrofuran under the protection of Ar gas 7.5mL, at 0℃, add 2M n-BuLi (1.1ml, 2.0eq), react for 20-30 minutes, add diisopropylphosphine chloride (2.2eq) with a syringe, continue to react for 1h, then raise the temperature naturally After reacting at room temperature for 24 hours, the solvent was spin-dried and subjected to basic alumina column chromatography (petroleum ether was used as eluent) to obtain 0.37 g of the product with a yield of 60.0%.

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Abstract

The invention provides a novel pure enantiomer amide type phosphinidene bidentate phosphine ligand with the structural formula shown on the right, wherein, the substituent R on the phosphorus atom of the bidentate phosphine ligand is alkyl or aryl. The synthetic methodsynthesis method is as follows: 4,4',6,6' -quadra (trifluoromethyl) biphenyl -2,2'- diamine is lithiated with n-butyllithium at -40 DEG C to 0 DEG C; then the lithiated 4,4',6,6' -quadra (trifluoromethyl) biphenyl-2,2'-diamine is reacted with dialkyl phosphonium chloride or diaryl phosphonium chloride, and heated naturally to room temperature and reacted for 12-24 hours to get the bidentate phosphine ligand through column chromatography. The invention takes chiral 4,4',6,6'-quadra(trifluoromethyl) - biphenyl -2,2'- diamine and various dialkyl phosphine chlorides or diphenyl(or substituted diphenyl group) phosphine chlorides as raw materials to prepare the amide type phosphinidene bidentate phosphine ligand. The invention enables the pure enantiomer amide type phosphinidene bidentate phosphine ligand to be applied to Rh-catalyzed ene amide and asymmetric hydrogenation of alpha-dehydro amino acid esters and achieves very good results, with the product enantioselectivity up to 99%.

Description

technical field [0001] The invention relates to a class of phosphonamidite bidentate phosphine ligands, a preparation method and application thereof. Background technique [0002] Chiral bisphosphine ligands have a very wide range of applications in asymmetric catalysis. Although a considerable number of chiral bisphosphine ligands with excellent properties have been reported, the synthesis of many bisphosphine ligands is difficult. [0003] The invention conveniently synthesizes a series of phosphonamidite type bidentate phosphine ligands, and uses them for asymmetric hydrogenation of enamide and asymmetric hydrogenation of α-dehydroamino acid ester, and can achieve very good results. Contents of the invention [0004] The object of the present invention is to provide a class of enantiomerically pure phosphonamidite type bidentate phosphine ligands, as well as their preparation method and use. Through the method provided by the invention, a series of bidentate phosphine...

Claims

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Application Information

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IPC IPC(8): C07F9/46B01J31/24B01J31/28C07C227/32C07C227/16C07B53/00
Inventor 王春江高锋陶海燕
Owner WUHAN UNIV
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