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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 for asymmetric catalytic reactions

Inactive Publication Date: 2002-06-19
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

[Yao, S.; Johannsen, M.; Audrain, H.; Hazell, R.G.; Jorgensen, K.A.J.Am.Chem.Soc.1998, 120, 8599-8650.] M.P.Doyle reported a class of chiral divalent rhodium catalysts In the catalytic hetero-Diels-Alder reaction, the highest TON reached 10,000, but the best enantioselectivity is only 80% ee [Doyle, M.P.; Phillips, I.M.; Hu, W.H.J.Am.Chem.Soc.2001, 123, 5366 .]

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 10

[0050] Embodiment ten or preparation of

[0051] In a dry 20mL Schlenk bottle filled with high-purity argon, add 6,6'-dimethyl-1,1'-binaphthol (0.04mmol) in R or S configuration, R or S configuration 6,6'-diphenyl-1,1'-binaphthol (0.04 mmol) and 10 mL of freshly distilled toluene (treated with sodium benzophenone free radical), stirred to dissolve the ligand completely. Inject Ti(O-iPr) with a microsyringe 4 Dichloromethane solution 80μL (0.04mmol, 0.5Min CH 2 Cl 2 ), followed by stirring at room temperature for 1 h to form a uniform transparent brown solution, which was stored at 0°C for future use. 1 H NMR (300MHz, CDCl 3 )δ=7.80-7.02(m, 30H, naphthalene ring), 4.05-3.92(m, 4H, 4(CH 3 ) 2 CHOH), 2.48(s, 6H), 1.62-1.41(bs, 4H, 4(CH 3 ) 2 CHOH), 1.21(d, J=6.1Hz, 24H, 4(CH 3 ) 2 CHOH).

Embodiment 11

[0052] Embodiment Eleven or preparation of

[0053] In a dry 20mL Schlenk bottle filled with high-purity argon, add R or S configuration 6,6'-dibromo-1,1'-binaphthol (0.04mmol), R or S configuration 6,6'-dimethoxy-1,1'-binaphthol (0.04 mmol) and 10 mL of freshly distilled toluene (treated with sodium benzophenone radical), stirred to dissolve the ligand completely. Inject Ti(O-iPr) with a microsyringe 4 Dichloromethane solution 80μL (0.04mmol, 0.5Min CH 2 Cl 2 ), followed by stirring at room temperature for 1 h to form a uniform transparent brown solution, which was stored at 0°C for future use. 1 H NMR (300MHz, CDCl 3 ) δ=7.86-6.95 (m, 20H, naphthalene ring), 4.05-3.92 (m, 4H, 4 (CH 3 ) 2 CHOH), 3.73(s, 6H), 1.60-1.43(bs, 4H, 4(CH 3 ) 2 CHOH), 1.20(d, J=6.1Hz, 24H, 4(CH 3 ) 2 CHOH). Example 12 L 2 -Ti-L 3 preparation of or

[0054] In a dry 20mL Schlenk bottle filled with high-purity argon, add R or S configuration 1,1'-binaphthol (0.04mol), R or S conf...

Embodiment 13

[0054] In a dry 20mL Schlenk bottle filled with high-purity argon, add R or S configuration 1,1'-binaphthol (0.04mol), R or S configuration 5,6,7,8- Tetrahydro-1,1'-binaphthol (0.04 mmol), 10 mL of freshly distilled toluene (treated with sodium benzophenone free radical), stirred to dissolve the ligand completely. Inject Ti(O-iPr) with a microsyringe 4 Dichloromethane solution 80μL (0.04mmol, 0.5M in CH 2 Cl 2 ), followed by stirring at room temperature for 1 h to form a uniform transparent brown solution, which was stored at 0°C for future use. 1 H NMR (300MHz, CDCl 3 )δ=8.15-6.85(m, 20H, naphthalene ring), 4.04-3.96(m, 4H, 4(CH 3 ) 2 CHOH), 2.83-2.78(m, 1H), 2.32-2.05(m, 3H), 1.78-1.58(m, 4H), 1.36(bs, 4H, 4(CH 3 ) 2 CHOH), 1.20(d, J=6.1Hz, 24H, 4(CH 3 ) 2 CHOH). Embodiment 13 or preparation of

[0055] In a dry 20mL Schlenk bottle filled with high-purity argon, add R or S configuration 6,6'-dimethyl-1,1'-binaphthol (0.04mol), R or S configuration 3-Bromo-5,6...

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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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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
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