Benzyl-position-substituted oxazoline phosphine ligand with chirality center, synthetic method and application

A technology of oxazoline and phosphine ligands, which is applied in the field of benzyl substituted oxazoline phosphine ligands, and can solve problems such as unsatisfactory results

Inactive Publication Date: 2007-08-08
SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

G.Helmchen and A.Pfaltz reported the application of benzene ring-derived oxazoline phosphine ligands (Acc.Chem.Res.2000, 33, 336) in asymmetric reactions

Method used

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  • Benzyl-position-substituted oxazoline phosphine ligand with chirality center, synthetic method and application
  • Benzyl-position-substituted oxazoline phosphine ligand with chirality center, synthetic method and application
  • Benzyl-position-substituted oxazoline phosphine ligand with chirality center, synthetic method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Example 1: Synthesis of Ligand P1

[0030] In a 100mL three-necked flask, 375mg (5mmol) of L-alaninol was dissolved in 40mL of THF, and n-BuLi (1.6M, 6.3mL, 10mmol) was added dropwise at 0°C. Lithiation was carried out at room temperature (22°C) for 1 hour after the addition was completed. 1.670g (5mmol) of 2-o-diphenylphosphobenzyl-4-isopropyl-4,5-dihydrooxazole was dissolved in 10mL THF, added dropwise to the above solution, heated to reflux for 27 hours, and obtained by column chromatography Corresponding amide compound; This amide compound is dissolved in 20mLCH 2 Cl 2, add 2.3mL (16.1mmol) of triethylamine, 0.25mL (3.22mmol) of trifluoromethanesulfonyl chloride, stir at room temperature for 24 hours, and separate by column chromatography, P1 is viscous liquid 895mg (72%);

[0031] P1(R 1 = R 2 = H, R 3 =CH 3 , Ar=Ph):

[0032] 1 H NMR (300MHz, CDCl 3 ): δ1.21(d, J=6.6Hz, 3H), 3.69-3.82(m, 2H), 3.88-4.05(m, 3H), 6.88-6.92(m, 1H), 7.14-7.38(m, 13H ); 31 P ...

Embodiment 2

[0039] Example 2: Synthesis of Ligand P5

[0040]

[0041] Under the protection of argon, (S)-2-(2-(2-bromophenyl)2-propyl)-4-isopropyl-oxazoline 997mg (3.24mmol) was dissolved in 15mLTHF, dry ice-acetone Cool the bath to -78°C, add n-BuLi2.31mL (3.70mmol) dropwise, lithiate at low temperature for 1 hour, add PPh dropwise at this temperature 2 Cl0.67mL (3.70mmol), after maintaining the low temperature for 30 minutes, remove the cold bath, rise to room temperature and react for 1 hour, quench the reaction with 15mL of saturated ammonium chloride, separate the organic layer, extract the aqueous layer with ether, and dry over anhydrous sodium sulfate , filtered, removed the solvent, and separated by column chromatography to obtain 876 mg of P5 as a white solid (66%).

[0042] P5(R 1 = R 2 =CH 3 ,R 3 =CH(CH 3 ) 2 , Ar=Ph):

[0043] 1 H NMR (300MHz, CDCl 3 ): δ0.76(d, J=7.0Hz, 3H), 0.84(d, J=7.0Hz, 3H), 1.73(m, 1H), 1.77(s, 3H), 1.84(s, 3H), 3.60 -3.70(m, 3H), 7.15-7....

Embodiment 3

[0058] Example 3: Synthesis of Ligands in Structure 2

[0059] With ligand P13 (n=0,, R 3 =CH(CH 3 ) 2 , the synthesis of Ar=Ph) is an example, completed by the following five-step reaction:

[0060]

[0061] 1.985g (10.1mmol) of o-bromophenylacetonitrile, 1.73mL (20.1mmol) of 1,2-dibromoethane were mixed and dissolved in 20mL MeCN, and 3.294g (10.2mmol) of n-tetrabutylammonium bromide was added under ice-water bath conditions, 50 % NaOH aqueous solution 20mL, stirred at room temperature for 1.5 hours, added 20mL of water, separated the organic layer, extracted the aqueous layer with ethyl acetate, dried over anhydrous sodium sulfate, filtered, spin-dried, and obtained 1-o-bromophenyl-1- Nitrile-cyclopropane white solid 1.840 g (82%);

[0062] 1 H NMR (300MHz, CDCl 3 ): δ1.25-1.39(m, 2H), 1.66-1.81(m, 2H), 7.16-7.34(m, 3H), 7.57-7.60(m, 1H); 13 C NMR (300MHz, CDCl 3 ): δ15.2, 16.6, 121.5, 126.3, 127.6, 130.1, 131.4, 133.1, 134.9; EI-MS m / z (relative intensity): 221 ...

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Abstract

The invention discloses an oxazoline phosphorus complexity, synthesizing method and application, which possesses chiral center substituted at benzyl position with structural formula as right formula, wherein the complexity can catalyze asymmetrical Heck reaction, asymmetrical allyl substituting reaction, asymmetrical aromatic hydrogenating reaction and kinds of insaturated base asymmetrical reaction.

Description

technical field [0001] The invention relates to a benzyl substituted oxazoline phosphine ligand, a synthesis method and application. The ligand has good applications in intermolecular asymmetric Heck reaction, asymmetric allyl substitution reaction, asymmetric aryl hydrogenation, asymmetric hydrogenation and other reactions. Background technique [0002] Oxazoline-phosphine ligands are an important class of N and P ligands, which have good applications in many metal-catalyzed asymmetric reactions. G.Helmchen and A.Pfaltz reported the application of benzene ring-derived oxazoline phosphine ligands (Acc.Chem.Res.2000, 33, 336) in asymmetric reactions, but the ligands were not used in asymmetric Heck reactions The results were not very satisfactory, especially in terms of ligand activity. Our group has done some work on improving the catalytic efficiency of ligands by changing the structure of ligands. Our group found that changing the coordinating atom directly connected to...

Claims

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Application Information

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IPC IPC(8): C07F9/653C07B53/00C07B35/02B01J31/24B01J31/30
Inventor 侯雪龙武文琼吕伟静
Owner SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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