通过去对称化/重排策略实现(-)-Hunterine A的对映选择性全合成。
Enantioselective Total Synthesis of (-)-Hunterine A Enabled by a Desymmetrization/Rearrangement Strategy.
作者信息
Hicks Elliot F, Inoue Kengo, Stoltz Brian M
机构信息
The 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.
出版信息
J Am Chem Soc. 2024 Feb 21;146(7):4340-4345. doi: 10.1021/jacs.3c13590. Epub 2024 Feb 12.
The first enantioselective total synthesis of (-)-hunterine A is disclosed. Our strategy employs a catalytic asymmetric desymmetrization of a symmetrical diketone and subsequent Beckmann rearrangement to construct a 5,6-α-aminoketone. A convergent 1,2-addition joins a vinyl dianion nucleophile and the enantioenriched ketone. The endgame of the synthesis features an aza-Cope/Mannich reaction and azide-olefin dipolar cycloaddition to complete the pentacyclic ring system. The synthesis is completed through a regioselective aziridine ring opening.
首次公开了(-)-hunterine A的对映选择性全合成。我们的策略采用对称二酮的催化不对称去对称化反应以及随后的贝克曼重排反应来构建一个5,6-α-氨基酮。一个汇聚式的1,2-加成反应将乙烯基双负离子亲核试剂与对映体富集的酮连接起来。合成的最后阶段采用氮杂-Cope/曼尼希反应和叠氮-烯烃偶极环加成反应来完成五环体系。通过区域选择性的氮丙啶开环反应完成了整个合成。
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