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Catalyst for catalyzing unsymmetrical hetero-Diels-Alder reaction, its preparation and application

A catalyst and reaction technology, applied in the field of new chiral catalysts and their preparation and asymmetric catalytic reactions, can solve the problem of low TON

Inactive Publication Date: 2004-04-21
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Hetero-Diels-Alder reaction is an important class of formation reactions of heterocyclic compounds, which can be used in the synthesis of many biologically active compounds, but it has not been applied in industry due to the low TON (Turnover Number)

Method used

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  • Catalyst for catalyzing unsymmetrical hetero-Diels-Alder reaction, its preparation and application
  • Catalyst for catalyzing unsymmetrical hetero-Diels-Alder reaction, its preparation and application
  • Catalyst for catalyzing unsymmetrical hetero-Diels-Alder reaction, its preparation and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Example 1 Synthesis of R-3-bromo-5,6,7,8-tetrahydro-1,1'-binaphthol

[0038]

[0039]R-5,6,7,8-tetrahydro-1,1'-binaphthol (290 mg, 1.0 mmol) and 6 mL of dry THF were added to a dry Schlenk bottle and the solid was dissolved with stirring. Under argon atmosphere, drop Br 2 (192mg, 1.2mmol), then stirred overnight at room temperature. After concentration, the reaction solution was separated on a silica gel column and eluted with ethyl acetate / n-hexane (1:7) to obtain 362 mg of white powder with a yield of 98.1%, m.p.90-92°C.[α] 25 D =+73.3 (C=1.08, CHCl 3 ).IR(KBr)ν max 3496,3058,2930,2858,1618,1596,1536,1452,1396,1342,1326,1312,1268,1238,1210,1190,1154,1132,1070,1022,962,944,912,866,818. 1 H NMR (400MHz, CDCl 3 )δ=7.87-7.82(m, 2H), 7.41-7.19(m, 5H), 5.13(s, 1H), 4.50(s, 1H), 2.79(t, J=6.3Hz, 2H), 2.25-2.04 (m, 2H), 1.74-1.27 (m, 4H). EIMS m / z (relative intensity): 368 (M + , 64.66), 43(100.00).HRMS(EI) caled for C 20 h 17 BrO 2 (M + ): 368.04119, found: 36...

Embodiment 2

[0040] Example 2 Synthesis of S-3-bromo-5,6,7,8-tetrahydro-1,1'-binaphthol

[0041]

[0042] R-5,6,7,8-tetrahydro-1,1'-binaphthol (290 mg, 1.0 mmol) and 6 mL of dry THF were added to a dry Schlenk bottle and the solid was dissolved with stirring. Under argon atmosphere, drop Br 2 (192mg, 1.2mmol), then stirred overnight at room temperature. After concentration, the reaction solution was separated on a silica gel column and eluted with ethyl acetate / n-hexane (1:7) to obtain 362 mg of white powder with a yield of 98.1%, m.p.90-92°C.[α] 25 D =-73.3° (C=1.08, CHCl 3 ).IR(KBr)ν max 3496,3058,2930,2858,1618,1596,1536,1452,1396,1342,1326,1312,1268,1238,1210,1190,1154,1132,1070,1022,962,944,912,866,818. 1 H NMR (400MHz, CDCl 3 )δ=7.87-7.82(m, 2H), 7.41-7.19(m, 5H), 5.13(s, 1H), 4.50(s, 1H), 2.79(t, J=6.3Hz, 2H), 2.25-2.04 (m, 2H), 1.74-1.27 (m, 4H). EIMS m / z (relative intensity): 368 (M + , 64.66), 43(100.00).HRMS(EI) caled for C 20 h 17 BrO 2 (M + ): 368.04119, found: ...

Embodiment 3

[0043] Example 3 Synthesis of R-3,3'-diphenyl-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthol

[0044]

[0045] 3,3'-diphenyl-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthol was prepared by a similar method referring to the literature [Cox, P.J. ; Wang, W.; Snieckus, V. Tetrahedron Lett., 1992, 33, 2253]. m.p.194-195℃.[α] 25 D =-29.3° (C=0.405, CHCl 3 ). 1 H NMR (300MHz, CDCl 3 )δ=7.57-7.54(m, 4H), 7.40-7.32(m, 4H), 7.30-7.22(m, 2H), 7.06(s, 2H), 4.85(s, 2H), 2.74(m, 4H) , 2.38-2.24(m, 2H), 2.22-2.14(m, 2H), 1.77-1.58(m, 8H).EIMS m / z(relative intensity): 446(M + , 100.00).HRMS(EI) caled for C 32 h 30 o 2 (M + ): 446.2246, found: 446.2220.

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Abstract

The present invention relates to a catalyst L-M-L'(in which L and L' represent chiral diphenol ligand and M represents central metal) formed from metal M and several kinds of chiral diphenol. Said catalyst can high-effectively catalyze asymmetric hetero-Diels-Alder reaction, its enantiomeric selectivity is up to 99.8% ee. TON(Turnover Number) is up to 12.720, so that it is a high-effective chiral Lewis acid catalysis system.

Description

technical field [0001] The invention relates to a novel chiral catalyst and its preparation and use in asymmetric catalytic reactions. Background technique [0002] Practical chemical synthesis is crucial to the sustainable development of human society, and the catalytic process is in an unshakable core position [R.Noyori, Adv.Synth.Catal.2001, 343, 1]. From the perspective of economy and environmental protection, asymmetric catalytic reactions provide an important way to meet the large demand for chiral substances in modern synthetic chemistry and medicinal chemistry. A very small amount of chiral catalysts can produce a large number of chiral substances through "chiral proliferation". sexual product. Catalysts for asymmetric catalytic reactions are divided into several categories, including enzymatic catalysis, organometallic catalysis, organic molecular catalysis, etc. Among them, organometallic catalysis is the most active research. Although chemists have prepared a va...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/22C07C39/00C07C39/15C07C39/21C07C39/225C07D309/10
Inventor 丁奎岭龙江胡婕妤
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI