Method of preparing chiral amine by catalytic hydrogenation of N- ulfimide by asymmetrical nickel

A technology of sulfonimide and chiral amine, which is applied in the field of asymmetric nickel-catalyzed hydrogenation of N-sulfonimide to prepare chiral amine, can solve the problems of heavy metal residues, limited application, high price, etc., and achieves mild conditions and easy operation. The effect of simplicity and good reaction yield

Active Publication Date: 2019-06-28
SHANGHAI JIAO TONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, this invention patent uses metal complexes of nails, rhodium, and iridium as catalysts, which are expensive, easily cause heavy metal residues, and cause large pollution, which greatly limits its application in industry

Method used

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  • Method of preparing chiral amine by catalytic hydrogenation of N- ulfimide by asymmetrical nickel
  • Method of preparing chiral amine by catalytic hydrogenation of N- ulfimide by asymmetrical nickel
  • Method of preparing chiral amine by catalytic hydrogenation of N- ulfimide by asymmetrical nickel

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050] 2a(R 1 = Ph, R 2 =CH 3 , R 2 = Preparation of t-Bu)

[0051] In a 10mL Schlenck tube, add phosphine ligand L1a (0.002mmol), nickel acetate tetrahydrate (0.5mg, 0.002mmol) and N-sulfonimide 1a (0.4mmol), the system was passed through the vacuum line and replaced with nitrogen for 3 Once, 1 mL of trifluoroethanol solvent was added and put into an autoclave. After 6 hydrogen replacements, the initial hydrogen pressure was 10 bar, and the reaction was stirred at 50°C for 24 hours. Cool, release gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion by NMR, and obtain the product by column chromatography. Yield 87%, enantiomeric excess 95%. 2a: white solid, 1 H NMR (400MHz, Chloroform-d) δ7.39-7.24(m, 5H), 4.67(dq, J=8.4, 6.8Hz, 1H), 4.55(s, 1H), 1.57(d, J=6.8Hz, 3H), 1.31(s, 9H); 13 C NMR (101MHz, Chloroform-d) δ143.8, 129.0, 127.7, 126.1, 60.0, 54.7, 25.9, 24.4.

Embodiment 2

[0053] 2a(R 1 = Ph, R 2 =CH 3 , R 3 = Preparation of t-Bu)

[0054] In a 10mL Schlenck tube, add phosphine ligand L1b (0.002mmol), nickel acetate tetrahydrate (0.5mg, 0.002mmol) and N-sulfonimide 1a (0.4mmol), the system was passed through the vacuum line and replaced with nitrogen for 3 Once, 1 mL of trifluoroethanol solvent was added and put into an autoclave. After 6 times of hydrogen replacement, the initial hydrogen pressure was 10 bar, and the reaction was stirred at 50°C for 24 hours. Cool, release gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion by NMR, and obtain the product by column chromatography. Yield 92%, enantiomeric excess 94%. 2a: white solid, 1 H NMR (400MHz, Chloroform-d) δ7.39-7.24(m, 5H), 4.67(dq, J=8.4, 6.8Hz, 1H), 4.55(s, 1H), 1.57(d, J=6.8Hz, 3H), 1.31(s, 9H); 13 C NMR (101MHz, Chloroform-d) δ143.8, 129.0, 127.7, 126.1, 60.0, 54.7, 25.9, 24.4.

Embodiment 3

[0056] 2a(R 1 = Ph, R 2 =CH 3 , R 3 = Preparation of t-Bu)

[0057] In a 10mL Schlenck tube, add phosphine ligand L1c (0.002mmol), nickel acetate tetrahydrate (0.5mg, 0.002mmol) and N-sulfonimide 1a (0.4mmol), the system was passed through the vacuum line and replaced with nitrogen for 3 Once, 1 mL of trifluoroethanol solvent was added, put into an autoclave, and after 6 hydrogen replacements, the initial hydrogen pressure was 10 bar, and the reaction was stirred at 50° C. for 24 hours. Cool, release gas carefully, open the autoclave, take out the vial, drain the solvent, detect the conversion by NMR, and obtain the product by column chromatography. Yield 95%, enantiomeric excess 95%. 2a: white solid, 1 H NMR (400MHz, Chloroform-d) δ7.39-7.24(m, 5H), 4.67(dq, J=8.4, 6.8Hz, 1H), 4.55(s, 1H), 1.57(d, J=6.8Hz, 3H), 1.31(s, 9H); 13 C NMR (101MHz, Chloroform-d) δ143.8, 129.0, 127.7, 126.1, 60.0, 54.7, 25.9, 24.4.

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Abstract

The invention discloses a method of preparing chiral amine by catalytic hydrogenation of N- sulfimide by asymmetrical nickel. The method comprises the following step: in a solvent, hydrogenating N-sulfimide shown in a formula (1) to a chiral amine compound shown in a formula (2) by catalysis of a chiral catalyst of nickel at a certain hydrogen pressure and temperature, wherein the structural formulae of the formulae (1) and (2) as shown in the description, The reaction method is mild in condition and simple to operate, can achieve good reaction yield and reaction efficiency, and has a relatively good application effect.

Description

technical field [0001] The invention relates to the technical field of chemical industry, in particular to a method for preparing chiral amine by asymmetric nickel-catalyzed hydrogenation of N-sulfonimide. Background technique [0002] Chiral amine compounds are useful skeletons in natural products, active molecules and some drugs, and are also effective chiral intermediates in the synthesis of some natural compounds and drugs, such as fendiline, rivastigmine, Inhibitors of cinacalcet, rasagiline IDH1 and CLK1, and some steroids, etc. This is a broad class of fundamental structures (Chiral Amine Synthesis: Methods, Developments and Applications (Ed.: T.C. Nugent), Wiley-VCH, Wcinheim, 2010). [0003] After searching the literature of the prior art, it is found that the general methods for obtaining such chiral compounds are extraction, resolution, biology or synthesis from chiral raw materials, which have great limitations and are uneconomical. [0004] At the same time, c...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D275/06C07D291/08C07D285/16C07C303/36C07C311/03C07C311/04C07C311/07C07B45/04
Inventor 张万斌陈建中李博闻张振锋
Owner SHANGHAI JIAO TONG UNIV
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