Palladium-Catalyzed anti-Michael Reductive Heck Reaction of α,β-Unsaturated Esters

Tao Guo,^a Yalan Ding,^a Lili Zhou,^a Haiyan Xu,^c Teck-Peng Loh,^ab* and Xiaojin Wu^a*

^a Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China

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

^c School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu 212003, China

Abstract: A general intermolecular anti-Michael reductive Heck reaction of α,β-unsaturated esters with organobromides has been developed. Most topical classes of aryl, heteroaryl, and vinyl bromides were found to efficiently react with a variety of internal conjugated alkenes. This protocol set up a platform toward diverse α-arylated 1,6-dicarbonyl frameworks found in natural products and drugs, which are still highly challenging targets in traditional α-arylation protocols because of competitive selectivity of enolation. A removable directing group, gram-scale reaction, and modification of complex molecules have additionally demonstrated that the anti-Michael reductive Heck reaction is a powerful complementary strategy to the classical α-arylation approaches. Preliminary mechanistic studies are consistent with our proposed mechanistic design.

ACS Catal. 2020, DOI: org/10.1021/acscatal.0c02414 (影响因子：12.221)

文章链接：https://doi.org/10.1021/acscatal.0c02414