Asymmetric Addition of 1-Ethynylcyclohexene to Ketones Catalyzed by a Chiral C2-Camphorsulfonamide Ligand

Chem. J. Chinese Universities

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Asymmetric Addition of 1-Ethynylcyclohexene to Ketones Catalyzed by a Chiral C₂-Camphorsulfonamide Ligand

ZHANG Dong-Yan, WANG Quan, CHEN Fu-Xin, YUAN Ye, WANG Rui^*

State Key Laboratory of Applied Organic Chemistry, Institute of Biochemistry and Molecular Biology, Lanzhou University, Lanzhou 730000, China

Received:2008-03-21 Revised:1900-01-01 Online:2008-09-10 Published:2008-09-10
Contact: WANG Rui

Abstract

Abstract: Addition of terminal alkynes to carbonyls is considered as an effective route for the synthesis of chiral propargyl alcohols and has gained a considerable significance in recent years. For possible further transformations of the alkene group, such as epoxidation, hydroxylation, ozonolysis, addition of carbenes, the asymmetric addition of 1-ethynylcyclohexene to ketones should have more potential applications than phenyla-cetylene for the synthesis of complex bioactive natural products. In this paper, the development of good enan-tioselective catalysts involving Cu(OTf)₂ and chiral C₂-camphorsulfonamide for the alkynylation of ketones including aromatic, heteroaromatic and aliphatic ketones was described. The reaction proceeded under mild conditions(toluene, room temperature) with the available catalyst. The reactions of aliphatic ketones could be completed in less than 12 h to give the products in good yields and enantioselectivities. The best enantioselectivity(up to 89% e.e.) was obtained in the alkynylation of 3-methylbutan-2-one. Moreover, the hindrance of the aliphatic ketones played a critical role in the control of the enantioselectivities of the corresponding pro-ducts.

Key words: C₂-Camphorsulfonamides, Asymmetric catalysis , 1-Ethynylcyclohexene

CLC Number:

O621.25
O643

TrendMD:

ZHANG Dong-Yan, WANG Quan, CHEN Fu-Xin, YUAN Ye, WANG Rui^*. Asymmetric Addition of 1-Ethynylcyclohexene to Ketones Catalyzed by a Chiral C₂-Camphorsulfonamide Ligand[J]. Chem. J. Chinese Universities, doi: .

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Asymmetric Addition of 1-Ethynylcyclohexene to Ketones Catalyzed by a Chiral C₂-Camphorsulfonamide Ligand

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