Double Activation Catalysis for α'-Alkylidene Cyclic Enones with Chiral Amines and Thiols

Chemistry : a European Journal
Zhou-Xiang WangYing-Chun Chen

Abstract

Cooperative catalysis has contributed greatly to the progress of asymmetric synthesis. However, double-activation catalysis has been less explored, especially for covalently tethered species. Here, we present a double-activation strategy for α'-alkylidene cyclic enone substrates that uses a chiral primary amine and 2-mercaptobenzoic acid to promote regio- and chemoselective addition to generate the complex interrupted iminium ion species. Significantly enhanced reactivity and enantioselectivity were observed for β-regioselective Michael addition and Friedel-Crafts alkylation with malononitriles and indoles, respectively, which produced a spectrum of chiral cyclic adducts with an exo-alkylidene group. Moreover, a HRMS study detected a few key covalently tethered intermediates among the substrates and catalysts, which helped elucidate the catalytic mechanism.

References

Feb 23, 2007·Organic & Biomolecular Chemistry·Wei ChenYing-Chun Chen
Jan 5, 2008·Organic & Biomolecular Chemistry·Xuefeng LiJingen Deng
Nov 6, 2012·Angewandte Chemie·Yao WangPeng-Fei Xu
Apr 26, 2016·Chemical Reviews·Kazimer L SkubiTehshik P Yoon
Jun 9, 2016·Journal of the American Chemical Society·Chang GuoFrank Glorius
Oct 21, 2016·Angewandte Chemie·Michael H Wang, Karl A Scheidt
Dec 16, 2016·Journal of the American Chemical Society·Xingyu JiangJohn F Hartwig
Jan 12, 2017·Journal of the American Chemical Society·Faben A Cruz, Vy M Dong
Mar 10, 2017·Chemical Communications : Chem Comm·Subin ChoiCheol-Min Park
Apr 22, 2017·Nature Chemistry·Rasmus MoseKarl Anker Jørgensen
May 26, 2017·Nature Chemistry·Zhi ZhouYing-Chun Chen

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