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N-sulfinyl amino acid amide compound and application thereof

A sulfinyl amino acid amide and compound technology, which is applied in the field of optically pure N-sulfinyl amino acid amide compounds to achieve good stereoselectivity

Inactive Publication Date: 2009-12-09
CHENGDU INST OF BIOLOGY CHINESE ACAD OF S
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the present invention, we have designed and synthesized a high enantioselective chiral organic small molecule catalyst with both thiochirality and carbon chirality for the first time, that is, N-sulfinyl amino acid amide compound, and successfully used it in Catalyzes the hydrogen transfer reduction reaction of trichlorosilane to imines. Compared with other existing chiral organic small molecule catalysts, this type of catalyst has a wider substrate universality, and can not only catalyze the high pair of N-aryl imines Enantioselective reduction, and more importantly, it can catalyze the highly enantioselective reduction of N-alkylimines, and there is no other chiral organic small molecule catalyst for the highly enantioselective reduction of the latter type of substrates can do

Method used

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  • N-sulfinyl amino acid amide compound and application thereof
  • N-sulfinyl amino acid amide compound and application thereof
  • N-sulfinyl amino acid amide compound and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Embodiment 1: the preparation of compound 1, structural formula is as follows:

[0027]

[0028] In a 100mL round bottom flask, add tetrahydrofuran (30mL), under argon protection, add N-Boc valine (1.3g, 6mmol), methyl iodide (9.1mL, 60mmol) and sodium hydride (2.53g, 60mmol) at zero . After the reaction was completed, add water to quench, evaporate the solvent under reduced pressure, add 50 mL of water to dissolve the residue, extract with ether, discard the organic phase, adjust the pH value of the aqueous phase to 3 with 1N hydrochloric acid, extract with ethyl acetate, combine the organic phase, After drying over magnesium sulfate, the solvent was evaporated under reduced pressure to obtain N-Boc-N-methylvaline as a colorless oil with a yield of 97%.

[0029] In a 50 mL round bottom flask, add the above colorless oil (200 mg, 0.86 mmol) and dichloromethane (5 mL), then add aniline (0.94 mL, 1.04 mmol), HOBt (153 mg, 1.04 mmol), DIEA (0.36 mL, 2.08mmol), EDCI (2...

Embodiment 2

[0032] Embodiment 2: the preparation of compound 2, structural formula is as follows:

[0033]

[0034] In a 50mL round bottom flask, add N-Boc-N-methylvaline (947mg, 4.1mmol) and dichloromethane (20mL), then add amantadine (500mg, 2.7mmol), HOBt (657.9mg , 4.05mmol), DIEA (1.12mL, 6.5mmol), EDCI (614mg, 3.2mmol). The reaction conditions, post-treatment method and subsequent removal of N-Boc protecting group and N-tert-butyl sulfonylation were the same as in Example 1 to obtain compound 2 as a white solid with a yield of 75%. 1 H NMR (300MHz, CDCl 3 ): δ (ppm) 6.07 (s, 1H), 3.26 (d, J = 8.76, 1H), 2.63 (s, 3H), 2.36-2.29 (m, 1H), 2.03 (s, 9H), 1.66 (s , 8H), 1.24(s, 9H), 0.90(d, J=6.66, 6H); 13 C NMR (75MHz, CDCl 3 ): δ (ppm) 168.8, 74.1, 59.5, 52.2, 41.2, 36.3, 29.4, 27.9, 27.8, 24.1, 20.5, 19.8; ESI HRMS (C 20 h 36 N 2 o 2 S 1 +Na) + The theoretical value is m / z 391.2390, and the measured value is m / z 391.2386.

Embodiment 3

[0035] Embodiment 3: the preparation of compound 3, structural formula is as follows:

[0036]

[0037] In a 50mL round bottom flask, add N-Boc-N-methylvaline (1.0g, 4.3mmol) and dichloromethane (30mL), then add p-fluoroaniline (0.35mL, 3.61mmol), HOBt ( 690mg, 4.69mmol), DIEA (1.5mL, 8.66mmol), EDCI (920mg, 4.69mmol), the reaction conditions and post-treatment methods and the subsequent removal of N-Boc protecting group and N-tert-butyl sulfonylation are the same as in the examples 1. Compound 3 was obtained as a white solid with a yield of 70%. 1 H NMR (300MHz, CDCl 3 ): δ (ppm) 9.06 (bs, 1H), 7.57-7.51 (m, 2H), 6.99-6.93 (m, 2H), 4.36 (d, J=7.05, 1H), 2.67 (s, 3H), 2.54 -2.44 (m, 1H), 1.33 (s, 9H), 1.09 (d, J=6.57, 3H), 1.03 (d, J=5.88, 3H); ESI HRMS (C 16 h 25 f 1 N 2 o 2 S 1 +Na) + The theoretical value m / z 351.1513, the measured value m / z 351.1517.

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Abstract

The invention discloses an optical pure N-sulfinyl amino acid amide compound and an application thereof, belonging to the technical field of organic chemistry. The optical pure N-sulfinyl amino acid amide compound has a structural formula shown in the right. Configurations of a sulfur atom and Cl are respectively R or S, wherein R and R are respectively an alkyl containing 1-25 of carbon atoms or an aryl containing 6-50 of carbon atoms; R is hydrogen or the alkyl containing 1-25 of carbon atoms or the aryl containing 6-50 of carbon atoms; R is a common pendant amino acid group comprising an annular pendant amino acid group forming a ring with the Cl, N and the R. The compound can selectively catalyze the hydrogen transfer reduction reaction of imine by trichlorosilane in three dimensions.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry, and relates to a chiral organic small molecular compound and its application in asymmetric catalysis, in particular to an optically pure N-sulfinyl amino acid amide compound and its application. Background technique [0002] Asymmetric organic small molecule catalysis is a new type of asymmetric catalytic method developed in recent years. Because the chiral organic small molecule catalyst used has the characteristics of simple structure, easy synthesis, low cost, simple production process, and environmental friendliness, The research in this field has attracted people's great attention (Angew.Chem., Int.Ed.2001, 40, 3726; Angew.Chem., Int.Ed.2004, 43, 5138; Org.Biomol.Chem.2005, 3,719). Chiral sulfur atoms are a class of very useful chiral sources, which have been widely used in chiral auxiliary agents and chiral ligands (Tetrahedron 2004, 60, 8033; Chem.Rev.2003, 103, 3651; Acc.Chem ...

Claims

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Application Information

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IPC IPC(8): C07C313/06C07D207/48C07D211/96B01J31/02C07C209/52
Inventor 孙健王超伍辛军
Owner CHENGDU INST OF BIOLOGY CHINESE ACAD OF S
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