导向的钯催化非共轭烯烃对氮杂环丁酮的对映选择性α-烷基化反应。
Catalytic, Enantioselective α-Alkylation of Azlactones with Nonconjugated Alkenes by Directed Nucleopalladation.
机构信息
Department of Chemistry, The Scripps Research Institute, 10550 N. Torrey Pines Road, BCC-169, La Jolla, CA, 92037, USA.
Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA, 15260, USA.
出版信息
Angew Chem Int Ed Engl. 2019 Mar 18;58(12):3923-3927. doi: 10.1002/anie.201814272. Epub 2019 Feb 27.
Abstract
A palladium(II)-catalyzed enantioselective α-alkylation of azlactones with nonconjugated alkenes is described. The reaction employs a chiral BINOL-derived phosphoric acid as the source of stereoinduction, and a cleavable bidentate directing group appended to the alkene to control the regioselectivity and stabilize the nucleopalladated alkylpalladium(II) intermediate in the catalytic cycle. A wide range of azlactones were found to be compatible under the optimal reaction conditions to afford products bearing α,α-disubstituted α-amino-acid derivatives with high yields and high enantioselectivity.
摘要
描述了钯（II）催化的非共轭烯烃与氮杂环丁酮的对映选择性α-烷基化反应。该反应采用手性 BINOL 衍生的磷酸作为立体诱导的来源，以及与烯烃连接的可裂解双齿导向基团，以控制区域选择性并稳定催化循环中的亲核钯化烷基钯（II）中间体。在最佳反应条件下，发现各种氮杂环丁酮都具有兼容性，可高收率和高对映选择性地得到带有α,α-二取代α-氨基酸衍生物的产物。
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