Achiral Pyridine Ligand-Enabled Enantioselective Radical Oxytrifluoromethylation of Alkenes with Alcohols
Achiral Pyridine Ligand-Enabled Enantioselective Radical Oxytrifluoromethylation of Alkenes with Alcohols
复制标题
非手性吡啶配体使烯烃与醇发生对映选择性自由基三氟甲基化
DOI：
10.1002/anie.201702925
复制
发表时间：
2017-07-17
影响因子：
16.6
通讯作者：
Liu, Xin-Yuan
中科院分区：
文献类型：
--
作者：
Cheng, Yong-Feng;Dong, Xiao-Yang;Liu, Xin-Yuan
在Cu-I/磷酸双催化下，以非手性吡啶为辅助配体稳定高价铜物种参与烯烃与醇的第一次不对称自由基氧三氟甲基化反应.该方法反应条件温和，底物范围广，官能团耐受性好，为合成具有α-叔位立构中心的三氟甲基取代四氢呋喃类化合物提供了一条有效途径，具有良好的对映选择性。机理研究支持假定的作用的非手性吡啶作为铜金属上的配位体，以稳定参与不对称诱导过程中的关键瞬态反应物种。
A conceptually novel strategy with achiral pyridine as the ancillary ligand to stabilize high-valent copper species for the first asymmetric radical oxytrifluoromethylation of alkenes with alcohols under Cu-I/phosphoric acid dual-catalysis has been developed. The transformation features mild reaction conditions, a remarkably broad substrate scope and excellent functional group tolerance, offering an efficient approach to a wide range of trifluoromethyl-substituted tetrahydrofurans bearing an a-tertiary stereocenter with excellent enantioselectivity. Mechanistic studies support the presumed role of the achiral pyridine as a coordinative ligand on copper metal to stabilize the key transient reaction species involved in the asymmetric induction process.