Palladium-Catalyzed Regiocontrollable Reductive Heck Reaction of Unactivated Aliphatic Alkenes

Chengdong Wang,^a Guanlin Xiao,^a Tao Guo,^a Yalan Ding,^a Xiaojin Wu^*,a and Teck-Peng Loh*^,ab

^a Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing 211816, P. R. China

^b Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637616

Abstract: A general Pd-catalyzed intermolecular reductive Heck reaction of both terminal and internal unactivated aliphatic alkenes has been firstly developed. This method affords γ- and δ-arylated alkyl carboxylic acid derivatives in high yields with complete anti-Markovnikov selectivity. Notably, the coupling process is stereoretentive for the alkyl chain. Mechanistically, alkyl palladacycle intermediates stabilized by directing group and ligand, hydride species multi-generated from PS/TFA reductant, are two key factors that successfully promote the reaction and regioselectivity.

JACS. 2018, DOI: 10.1021/jacs.8b03619 (2017年影响因子: 13.858，第一作者为硕士研究生王成东).

论文链接：https://pubs.acs.org/doi/pdf/10.1021/jacs.8b03619