文献类型：期刊文献

英文题名：Regioselective and diastereodivergent organocatalytic asymmetric vinylogous Michael addition

作者：Zou, Chuncheng[1,2];Lv, Yanting[1];Lu, Min[1];Li, Xin[1];Zhang, Lei[1];Yang, Lei[1];Liu, Zhen[3];Ke, Yanxiong[1];Song, Gonghua[2];Ye, Jinxing[1]

机构：[1]East China Univ Sci & Technol, Sch Pharm, Minist Educ, Engn Res Ctr Pharmaceut Proc Chem, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Pharm, Shanghai Key Lab Chem Biol, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, State Key Lab Chem Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2021

卷号：8

期号：17

起止页码：4758

外文期刊名：ORGANIC CHEMISTRY FRONTIERS

收录：;EI(收录号：20213510835714);WOS:【SCI-EXPANDED(收录号:WOS:000665180500001)，CCR-EXPANDED(收录号:WOS:000665180500001)】；

基金：This work was supported by the National Natural Science Foundation of China (21272068, 21572056, and 21801077), the China Postdoctoral Science Foundation (2017M621382 and 2018T110355), the Shanghai Sailing Program (18YF1406200), and the Fundamental Research Funds for the Central Universities. We thank the Research Center of Analysis and Test of East China University of Science and Technology and Prof. Z. Li's group for their help with NMR and MS analyses.

语种：英文

外文关键词：Stereoselectivity - Addition reactions - Regioselectivity - Hydrogen bonds

摘要：Regioselective and diastereodivergent asymmetric vinylogous Michael addition (AVMA) between beta-substituted-cyclohexenones and nitroalkenes via dienamine activation under complementary chiral aminocatalysts was reported. gamma-Regioselective AVMA of beta-alkyl-cyclohex-2-enones via a linear exo-dienamine mechanism and gamma '-regioselective functionalization of beta-substituted-cyclohex-3-enones via a cyclic extended endo-dienamine mechanism were reported in satisfactory yields with high enantio- and diastereoselectivities. DFT calculations reasonably explained that the diastereoselectivity of the reactions at the gamma- and gamma '-positions is achieved by regulating the orientation of the nitroalkenes through the hydrogen-bonding interaction and steric hindrance effect. Furthermore, the four different configurations of the gamma- and gamma '-adducts were diversified to the corresponding enantioenriched spirocyclic ketones and cis-2-decalones with multiple chiral centers.