铜催化的烯丙醇对映选择性羟烷化反应合成环状醚。
Copper-Catalyzed Enantioselective Hydroalkoxylation of Alkenols for the Synthesis of Cyclic Ethers.
机构信息
Chemistry Department, State University of New York at Buffalo, Buffalo, New York 14260, United States.
出版信息
Org Lett. 2020 Oct 2;22(19):7409-7414. doi: 10.1021/acs.orglett.0c01691. Epub 2020 Jun 4.
Abstract
The copper-catalyzed enantioselective intramolecular hydroalkoxylation of unactivated alkenes for the synthesis of tetrahydrofurans, phthalans, isochromans, and morpholines from 4- and 5-alkenols is reported. The substrate scope is complementary to existing enantioselective alkene hydroalkoxylations and is broad with respect to substrate backbone and alkene substitution. The asymmetric induction and isotopic labeling studies support a polar/radical mechanism involving enantioselective oxycupration followed by C-[Cu] homolysis and hydrogen atom transfer. Synthesis of the antifungal insecticide furametpyr was accomplished.
摘要
报道了铜催化的非活化烯烃的对映选择性分子内烷氧基化反应，用于从 4-和 5-烯醇合成四氢呋喃、酞嗪、异茨醇和吗啡啉。该底物范围与现有的对映选择性烯烃烷氧基化反应互补，并且在底物骨架和烯烃取代基方面具有广泛的适用性。不对称诱导和同位素标记研究支持涉及对映选择性氧铜化的极性/自由基机理，然后是 C-[Cu]均裂和氢原子转移。完成了杀真菌杀虫剂呋虫胺的合成。
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