Chiral compound having multi-hydrogen bonds dual-function as well as synthetic method and use thereof

A chiral compound and dual-functional technology, which is applied in organic chemical methods, preparation of organic compounds, organic compound/hydride/coordination complex catalysts, etc., can solve the problem of high catalyst usage and limited substrate application range, etc. problem, to achieve the effect of fast catalytic reaction speed, low catalyst dosage and good enantioselectivity

Inactive Publication Date: 2008-07-23
常熟紫金知识产权服务有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Bifunctional chiral thiourea catalysts can catalyze the asymmetric Michael addition reaction of ketones or esters with nitroalkenes. Although people have done a lot of research work, the use of existing chiral thiourea catalysts can only be used for specific The substrates show a certain catalytic activity and enantioselectivity, the scope of application of the substrate is not wide, and the amount of catalyst used is generally relatively high

Method used

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  • Chiral compound having multi-hydrogen bonds dual-function as well as synthetic method and use thereof
  • Chiral compound having multi-hydrogen bonds dual-function as well as synthetic method and use thereof
  • Chiral compound having multi-hydrogen bonds dual-function as well as synthetic method and use thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Example 1: Preparation of catalyst: 1-((1R, 2R)-2-(dimethylamino)cyclohexyl)-3-((1R, 2R)-1,2-diphenyl-2-(methyl Sulfonamide) ethyl) thiourea

[0021]

[0022] Add (1R,2R)-2-isothiocyanato-N,N-dimethylcyclohexylamine (24mg, 0.13mmol) to a solution of (1R,2R)-1,2-diphenyl A solution of N-methylsulfonyl-1,2-ethylenediamine (37 mg, 0.13 mmol) in dry tetrahydrofuran (1 mL) was stirred at room temperature for 12 hours. After distilling the solvent to dryness, the mixture was subjected to silica gel column chromatography to obtain the product. Yield 97%. Mp 240-241°C; [α] 25 D +9.4° (c0.44, CHCl 3 ); IR (KBr) 3400, 1675, 1595, 1500, 1445, 1270, 1040, 965, 670cm-1; 1 H NMR (CDCl 3 , TMS, 300MHz) δ1.21-1.24(m, 4H), 1.69-1.90(m, 4H), 2.20(m, 1H), 2.41(s, 6H), 2.47(s, 3H), 3.70(m, 1H), 4.79(d, J=10.2Hz, 1H), 5.88(s, 1H), 7.08-7.22(m, 10H); 13 C NMR (CDCl 3 , TMS, 75MHz) δ22.65, 24.37, 24.52, 32.59, 39.86, 41.69, 55.24, 62.25, 64.38, 66.34, 127.64, 127.76, 128.44, 128....

Embodiment 2

[0023] Example 2: Preparation of catalyst: 1-((1R, 2R)-2-(dimethylamino)cyclohexyl)-3-((1S, 2S)-1,2-diphenyl-2-(p Tosylamide) ethyl) thiourea

[0024]

[0025] Add (1R,2R)-2-isothiocyanato-N,N-dimethylcyclohexylamine (40.23mg, 0.22mmol) to a solution of (1S,2S)-1,2-di A solution of phenyl-N-p-toluenesulfonyl-1,2-ethylenediamine (120 mg, 0.33 mmol) in dry THF (2 mL) was stirred at room temperature for 12 hours. After distilling the solvent to dryness, the mixture was subjected to silica gel column chromatography to obtain the product. Yield 85%. Mp.110-113℃; [α] 25 D +18.5 (c 0.62, CHCl 3 ); IR(KBr)v 3357, 3062, 3030, 2932, 2858, 1536, 1327, 1155cm -1 ; 1 H NMR (CDCl 3 , TMS, 300MHz) δ1.08-1.29(m, 4H), 1.63-1.76(m, 3H), 1.95(s, 6H), 2.20(m, 1H), 2.25(s, 3H), 2.42(m, 1H), 3.58(m, 1H), 4.70(d, J=10.2Hz, 1H), 5.68(m, 1H), 6.86-7.13(m, 12H), 7.41(d, J=8.1Hz, 2H); 13 C NMR (CDCl 3 , TMS, 75MHz) δ21.59, 22.37, 24.79, 25.17, 33.41, 40.13, 56.67, 62.99, 63.84, 67.25, 127....

Embodiment 3

[0026] Example 3: Preparation of catalyst: 1-((1R, 2R)-2-(dimethylamino)cyclohexyl)-3-((1R, 2R)-1,2-diphenyl-2-(p Tosylamide) ethyl) thiourea

[0027]

[0028] Add (1R,2R)-2-isothiocyanato-N,N-dimethylcyclohexylamine (40.23mg, 0.22mmol) to a solution of (1R,2R)-1,2-di A solution of phenyl-N-p-toluenesulfonyl-1,2-ethylenediamine (80 mg, 0.22 mmol) in dry THF (2 mL) was stirred at room temperature for 12 hours. After distilling the solvent to dryness, the mixture was subjected to silica gel column chromatography to obtain the product. Yield 80%. Mp.240-241℃; [α] 25 D +3.5°(c0.62, CHCl 3 ); IR (KBr) 3400, 1675, 1595, 1500, 1445, 1270, 1040, 965, 670cm-1; 1 HNMR (CDCl 3 , TMS, 300MHz) δ1.18-1.27(m, 4H), 1.68-1.90(m, 3H), 2.30(s, 1H), 2.35(s, 6H), 2.20-2.43(m, 2H), 3.47( s, 1H), 4.72(d, J=10.8Hz, 1H), 5.81(m, 1H), 6.86-7.21(m, 12H), 7.40(d, J=10.8Hz, 2H); 13 C NMR (CDCl 3 , TMS, 75MHz) δ21.67, 22.88, 24.76, 25.11, 32.89, 41.29, 56.85, 63.04, 64.79, 67.17, 126.99, 127.3...

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PUM

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Abstract

The invention relates to a multi-hydrogen bond and bifunctional chiral compound with right-hand structure; wherein, the X is oxygen or sulfur; R[1] and R[2] are - (CH2)4- or R[1] and R[2] are respectively aryl; R[3] and R[4] are - (CH2)4 or aryl or R[3] and R[4] are respectively alkyl, benzyl or aryl selected from H, C1 to C6; R[5] is methyl, fluorine-containing alkane or aryl. The multi-hydrogen bond and bifunctional chiral compound is characterized in that: chiral compounds with isothiocyanate ester group or chiral compounds of the isothiocyanate ester group, 1, 2-o- diamine derivative and 1, 2-amino alcohol or phenol derivatives are reacted at dry ethers or halogenated hydrocarbon solventthrough stirring at ambient temperature, thereby getting the multi-hydrogen bond and bifunctional chiral compounds. The multi-hydrogen bond and bifunctional chiral compounds can be applied in unsymmetrical michael addition reaction as catalyst and enantio-selectivity reaches 99%.

Description

technical field [0001] The invention relates to a bifunctional chiral compound with multiple hydrogen bonds, its synthesis method and its application in asymmetric reaction. Background technique [0002] Chiral thiourea compounds are an important class of organic small molecule catalysts, which exhibit very high chiral induction ability in many asymmetric organocatalytic reactions ((a) S.B.Tsogoeva, Eur.J.Org.Chem.2007, 1701; (b) Y. Takemoto, Org. Biomol. Chem. 2005, 3, 4299; (c) S. J. Connon, Chem.-Eur. J. 2006, 12, 5418.)). The currently reported chiral thiourea catalysts generally use chiral cyclohexanediamine as the skeleton, and different chiral or achiral skeletons are connected through thiourea groups. Recently, many new bifunctional chiral thioureas have been synthesized and exhibit high catalytic activity and enantioselectivity in many asymmetric reactions. [0003] Bifunctional chiral thiourea catalysts can catalyze the asymmetric Michael addition reaction of ket...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C335/14C07C335/12B01J31/02C07C201/12C07C205/45C07C205/50C07B53/00
Inventor 王春江张志海董秀琴陶海燕
Owner 常熟紫金知识产权服务有限公司
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