β,γ-Vicinal Dicarbofunctionalization of Alkenyl Carbonyl Compounds via Directed Nucleopalladation
β,γ-Vicinal Dicarbofunctionalization of Alkenyl Carbonyl Compounds via Directed Nucleopalladation
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DOI：
10.1021/jacs.6b09170
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发表时间：
2016-11-23
影响因子：
15
通讯作者：
Engle, Keary M.
中科院分区：
文献类型：
--
作者：
Liu, Zhen;Zeng, Tian;Engle, Keary M.
已开发了钯（II）催化的未活化烯烃的1，2-二碳官能化反应，其中可裂解的双齿导向基团用于控制区域选择性和稳定推定的烷基钯（II）中间体。在优化的反应条件下，广泛的亲核试剂和亲电试剂被发现参与这种转化，提供中到高的产率。3-丁烯酸衍生物含有内烯烃和α-取代基，反应底物，提供了一个强大的平台，制备β，γ-取代的羰基化合物与多个立体中心。
A palladium(II)-catalyzed 1,2-dicarbofunctionalization reaction of unactivated alkenes has been developed, wherein a cleavable bidentate directing group is used to control the regioselectivity and stabilize the putative alkylpalladium(II) intermediate. Under the optimized reaction conditions, a broad range of nucleophiles and electrophiles were found to participate in this transformation, providing moderate to high yields. 3-Butenoic acid derivatives containing internal alkenes and a-substituents were reactive substrates, offering a powerful platform for preparing beta,gamma-substituted carbonyl compounds with multiple stereocenters.