Ni Huanzhen, Wong Yee Lin, Wu Mingyue, Han Zhaobin, Ding Kuiling, Lu Yixin
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore.
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
Org Lett. 2020 Mar 20;22(6):2460-2463. doi: 10.1021/acs.orglett.0c00681. Epub 2020 Mar 10.
We report a highly enantioselective [3 + 2] annulation between 3-butynoates and β-trifluoromethyl enones, furnishing trifluoromethylated cyclopentenes with three contiguous stereogenic centers in good yields, high diastereoselectivities, and excellent enantioselectivities. A unique catalytic system consisting of a simple amine and a chiral phosphine was devised, and the synergistic play of Lewis basic amine and phosphine was crucial for alkyne isomerization and subsequent cyclization. The protocol disclosed herein allows facile activation of 3-butynoates in phosphine-mediated asymmetric transformations.
我们报道了3-丁炔酸酯与β-三氟甲基烯酮之间的高度对映选择性[3 + 2]环化反应，以良好的产率、高非对映选择性和优异的对映选择性提供具有三个相邻立体ogenic中心的三氟甲基化环戊烯。设计了一种由简单胺和手性膦组成的独特催化体系，Lewis碱性胺和膦的协同作用对于炔烃异构化和随后的环化至关重要。本文公开的方法允许在膦介导的不对称转化中轻松激活3-丁炔酸酯。
