Copper(I)-Catalyzed Regioselective Asymmetric Addition of 1,4-Pentadiene to Ketones

作者：Feng Zhong, Zhi‐Zhou Pan, Siwei Zhou, Haijun Zhang, Liang Yin · 发表于：Journal of the American Chemical Society · 年份：2021 · DOI：10.1021/jacs.1c02084 · 被引用次数：32 · 研究领域：Synthetic Organic Chemistry Methods、Asymmetric Synthesis and Catalysis、Organoboron and organosilicon chemistry

By using commercially available 1,4-pentadiene as a pronucleophile, a copper(I)-catalyzed regioselective asymmetric allylation of ketones is achieved. A variety of chiral tertiary alcohols bearing a terminal ( Z )-1,3-diene unit are generated in high ( Z )/( E ) ratio and high enantioselectivity. Both aromatic ketones and aliphatic ketones serve as suitable substrates. Furthermore, the reactions with ( E )-C 1 (alkyl)-1,4-dienes proceed in moderate yields with acceptable enantioselectivity but with low ( Z, E )/others ratio, which demonstrates the partial isomerization of ( E )-allylcopper(I) species to ( Z )-allylcopper(I) species through 1,3-migration. Subsequent Heck reaction and olefin metathesis compensate for the low efficiency with C 1 -1,4-dienes. The synthetic utility of the product is further demonstrated by a copper(I)-catalyzed regioselective borylation of the 1,3-diene group.