手性烯丙基酮的对映选择性 Conia-Ene 型环化反应通过 B(CF₅)₃、N-烷基胺和锌基催化剂的协同作用。
Enantioselective Conia-Ene-Type Cyclizations of Alkynyl Ketones through Cooperative Action of B(CF), N-Alkylamine and a Zn-Based Catalyst.
机构信息
Department of Chemistry, Merkert Chemistry Center , Boston College , Chestnut Hill , Massachusetts 02467 , United States.
出版信息
J Am Chem Soc. 2019 Mar 13;141(10):4199-4203. doi: 10.1021/jacs.8b13757. Epub 2019 Feb 27.
Abstract
An efficient and highly enantioselective Conia-ene-type process has been developed. Reactions are catalyzed by a combination of B(CF), an N-alkylamine and a BOX-ZnI complex. Specifically, through cooperative action of B(CF) and amine, ketones with poorly acidic α-C-H bonds can be converted in situ to the corresponding enolates. Subsequent enantioselective cyclization involving a BOX-ZnI-activated alkyne leads to the formation of various cyclopentenes in up to 99% yield and 99:1 er.
摘要
已开发出一种高效且高度对映选择性的 Conia-ene 型反应。该反应由 B(CF₅)₃、N-烷基胺和 BOX-ZnI 配合物共同催化。具体而言，通过 B(CF₅)₃和胺的协同作用，可将酸性较弱的α-C-H 键酮原位转化为相应的烯醇化物。随后，涉及 BOX-ZnI 活化的炔烃的对映选择性环化反应导致各种环戊烯以高达 99%的产率和 99:1 的对映选择性形成。
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