Bifunctional chiral sacchariferous semicarbazide and thiocarbamide catalyst and its prepn process and application in asymmetric reaction

A chiral catalyst and dual-functional technology, applied in chemical instruments and methods, preparation of organic compounds, physical/chemical process catalysts, etc., can solve problems such as inability to obtain ideal results for substrates, and achieve high stereoselective effects

Inactive Publication Date: 2007-06-06
TIANJIN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] Chiral urea and thiourea catalysts are used for the condensation reaction of nitroalkanes and aldehydes and ketones and the addition reaction of ketones containing active hydrogen at the α position to nitroalkenes. Although a lot of research work has been done, the use of existing chiral Urea and thiourea catalysts can only show high activity and enantioselectivity for specific substrates, and cannot obtain ideal results for all substrates

Method used

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  • Bifunctional chiral sacchariferous semicarbazide and thiocarbamide catalyst and its prepn process and application in asymmetric reaction
  • Bifunctional chiral sacchariferous semicarbazide and thiocarbamide catalyst and its prepn process and application in asymmetric reaction
  • Bifunctional chiral sacchariferous semicarbazide and thiocarbamide catalyst and its prepn process and application in asymmetric reaction

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0031] Example 1: Preparation of catalyst: N-(1R, 2R)-(2-aminocyclohexyl)-N'-(2',3',4',6'-tetra-O-acetyl-β-D- Glucopyranosyl-1'-)thiourea

[0032]

[0033] At room temperature, 1.14 g (3 mmol) of 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl isothiocyanate was added to dissolve 0.41 g (3.6 mmol) (1R, 2R)-cyclohexanediamine in dichloromethane (20 mL), and then the mixture was reacted at the same temperature for 6 hours. After the solvent was distilled off, the mixture was subjected to silica gel column chromatography using ethyl acetate / triethylamine (volume ratio 100 / 1) as the eluent to obtain the crude product. At 0-5°C, dissolve it with as little dichloromethane as possible. After slowly adding petroleum ether (60-90°C), the required chiral thiourea catalyst is precipitated with a yield of 61%, [α] D 20 +43.1°(c 1.0, CHCl 3 ), 1 H NMR(500MHz, CDCl 3 )δ5.82(m, 1H), 5.21(d, J=80Hz, 4H), 4.30-3.83(m, 4H), 3.48(m, 1H), 2.00-2.09(m, 14H).1.72(m, 3H), 1.26 (m, 5H), 0.93 (m, 1H); IR (KB...

example 2

[0034] Example 2: Preparation of catalyst: N-(1R, 2R)-(2-aminocyclohexyl)-N'-(2', 3', 4', 6'-tetra-O-acetyl-β-D- Glucopyranosyl-1'-)thiourea

[0035]

[0036] At room temperature, 1.14 g (3mmol) 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosylamine was added to dissolve 0.41 g (3.6mmol) (1R, 2R)-1 -Amino-2-iso(thio)hydrocyclohexane in dichloromethane (20 mL), and then the mixture was reacted at 40°C for 2 hours. After the solvent was distilled off, the mixture was subjected to silica gel column chromatography using ethyl acetate / triethylamine (volume ratio 100 / 1) as the eluent to obtain the crude product. At 0-5°C, dissolve it with as little dichloromethane as possible. After slowly adding petroleum ether (60-90°C), the required chiral thiourea catalyst is precipitated with a yield of 52%, [α] D 20 +43.1°(c 1.0, CHCl 3 ),1 HNMR(500MHz, CDCl 3 )δ 5.82 (m, 1H), 5.21 (d, J = 80Hz, 4H), 4.30-3.83 (m, 4H), 3.48 (m, 1H), 2.00-2.09 (m, 14H), 1.72 (m, 3H), 1.26 (m, 5H), 0.93 (m, 1H); IR (KBr)...

example 3

[0037] Example 3: Preparation of catalyst: N-(1R, 2R)-(2-aminocyclohexyl)-N'-(2', 3', 4', 6'-tetra-O-pivaloyl-β-D -Glucopyranosyl-1'-)thiourea

[0038]

[0039] Synthesis of N-(1R,2R)-(2-aminocyclohexyl)-N'-(2',3',4',6'-tetra-O-pivaloyl-β-D by a method similar to Example 1 -Glucopyranosyl-1'-)thiourea, the yield is 33%, [α] D 20 +63.1°(c 1.0, CHCl 3 )

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Abstract

The present invention relates to one kind of bifunctional chiral catalyst container sacchariferous semicarbazide and thiocarbamide and its preparation process and application in asymmetry reaction. The preparation process includes: the reaction of saccharide with NCX or NH radical and ethamide with NH2 or NCX radical in the 2-position in organic solvent at 20-110 deg.c for 3-24 hr, evaporation to eliminate solvent and separation in a silica gel column to obtain the product. The molar ratio between saccharide with NCX or NH radical and ethamide with NH2 or NCX radical in the 2-position is 1 to 1-1.5. The bifunctional chiral catalyst has wide application, may be used in condensation reaction, addition reaction, etc. and has very high stereo selectivity and i.e. value up to 98 %.

Description

Technical field [0001] The present invention relates to a new type of bifunctional semicarbazide and thiourea bifunctional organic small molecule catalyst with a chiral sugar-containing structure, and specifically discloses a bifunctional chiral sugar-containing semicarbazide and thiourea catalyst and a preparation method thereof. Application in asymmetric reactions. Background technique [0002] Chiral urea and thiourea compounds are an important class of organic small molecule catalysts, which exhibit very efficient chirality inducing ability in many organic catalytic asymmetric reactions (Stephen J. Connon, Chem. Eur. J 2006, 12, 5418-5427). The currently reported chiral urea and thiourea catalysts generally use chiral cyclohexanediamine as the skeleton, and then connect different chiral skeletons through urea and thiourea groups, such as small molecular peptide chains, chiral binaphthyl, and chiral Cinchona and so on. Recently, many new chiral ur...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/18C07B37/02C07C201/12C07C205/45C07D307/40C07H5/04
Inventor 马军安刘昆崔汉峰聂晶董科研李小娟
Owner TIANJIN UNIV
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