手性钯催化的噻喃酮的脱羧烯丙基烷基化反应。非环状、立体手性α-季碳酮的合成。
Enantioselective Pd-Catalyzed Decarboxylative Allylic Alkylation of Thiopyranones. Access to Acyclic, Stereogenic α-Quaternary Ketones.
机构信息
Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology , Pasadena, California 91125, United States.
Department of Molecular Engineering, Therapeutic Discovery, Amgen, Inc. , 1 Amgen Center Drive, M/S 29-M-B, Thousand Oaks, California 91320, United States.
出版信息
Org Lett. 2017 Oct 6;19(19):5007-5009. doi: 10.1021/acs.orglett.7b02354. Epub 2017 Sep 13.
Abstract
A catalytic, enantioselective decarboxylative allylic alkylation of 4-thiopyranones is reported. The α-quaternary 4-thiopyranones produced are challenging to access by standard enolate alkylation owing to facile ring-opening β-sulfur elimination. In addition, reduction of the carbon-sulfur bonds provides access to elusive acyclic α-quaternary ketones. The alkylated products are obtained in up to 92% yield and 94% enantiomeric excess.
摘要
本文报道了一种催化的、对映选择性的 4-噻喃酮的脱羧烯丙基烷基化反应。由于易于开环β-硫消除，标准烯醇化物烷基化难以获得产生的α-季铵 4-噻喃酮。此外，碳-硫键的还原提供了获得难以捉摸的非环α-季铵酮的途径。烷基化产物的产率高达 92%，对映体过量值高达 94%。
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