文献类型：期刊文献

英文题名：Diastereodivergent organocatalytic asymmetric vinylogous Michael reactions

作者：Li, Xin[1];Lu, Min[1];Dong, Yun[1];Wu, Wenbin[1];Qian, Qingqing[1];Ye, Jinxing[1];Dixon, Darren J.[2]

机构：[1]E China Univ Sci & Technol, Sch Pharm, Shanghai Key Lab New Drug Design, Shanghai 200237, Peoples R China;[2]Univ Oxford, Chem Res Lab, Dept Chem, Oxford OX1 3TA, England

年份：2014

卷号：5

外文期刊名：NATURE COMMUNICATIONS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000340623400024)】；

基金：This work was partially supported by National Natural Science Foundation of China (21272068), Program for New Century Excellent Talents in University (NCET-13-0800), Innovation Program of Shanghai Municipal Education Commission (11ZZ56), the 111 Project (Grant B07023) and the Fundamental Research Funds for the Central Universities and the EPSRC (Leadership Fellowship to D.J.D.).

语种：英文

摘要：One of the major challenges of modern asymmetric catalysis is the ability to selectively control the formation of all diastereoisomers of reaction products possessing multiple stereocenters. Pioneers of such diastereodivergent catalytic asymmetric processes have focused on reactions where the newly formed stereogenic centres are proximal to the active carbonyl group. To date, however, diastereodivergent reactions at remote positions remain an unmet challenge. Herein, we describe a catalyst-controlled diastereodivergence in the formation of remote stereocenters in the direct vinylogous Michael reactions of beta, gamma-unsaturated butenolides to alpha, beta-unsaturated ketones. The reactions are enabled by two complementary, non-enantiomeric multifunctional catalysts, which mutually activate and organise both reactants, affording either the syn- or anti-adduct with high diastereo- and enantioselectivity. These two catalytic systems are also applicable in the Mukaiyama-Michael reactions and tandem Michael-Michael reactions.