β,γ-Vicinal Dicarbofunctionalization of Alkenyl Carbonyl Compounds via Directed Nucleopalladation

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 α-substituents were reactive substrates, offering a powerful platform for preparing β,γ-substituted carbonyl compounds with multiple stereocenters.本研究开发了一种钯(II)催化的非活化烯烃（unactivated alkenes）1,2-双碳官能化（1,2-dicarbofunctionalization）反应体系，采用可裂解双齿导向基（cleavable bidentate directing group）控制反应区域选择性（regioselectivity），并稳定推测得到的烷基钯(II)中间体（alkylpalladium(II) intermediate）。在优化后的反应条件下，该转化可兼容多种类亲核试剂（nucleophiles）与亲电试剂（electrophiles）参与，产物收率可达中等至优异水平。含内烯烃（internal alkenes）与α-取代基（α-substituents）的3-丁烯酸衍生物（3-Butenoic acid derivatives）均可作为活性底物，为构建含多手性中心（multiple stereocenters）的β,γ-取代羰基化合物（β,γ-substituted carbonyl compounds）提供了高效合成平台。