A computationally designed Rh(I)-catalyzed two-component [5+2+1] cycloaddition of ene-vinylcyclopropanes and CO for the synthesis of cyclooctenones

作者:Wang Yuanyuan; Wang Jingxin; Su Jiachun; Huang Feng; Jiao Lei; Liang Yong; Yang Dazhi; Zhang Shiwei; Wender Paul A; Yu Zhi Xiang*
来源:Journal of the American Chemical Society, 2007, 129(33): 10060-+.
DOI:10.1021/ja072505w

摘要

Through the combined use of computational (density functional theory) and experimental studies, a new [Rh(CO)(2)Cl](2) catalyzed two-component [5+2+1] cycloaddition of ene-vinylcyclopropanes and CO for the synthesis of fused bicyclic cyclooctenones has been designed and experimentally realized. The key point behind this design is to turn a disfavored reductive elimination of (sp(3))C-Rh-C(sp(3)) to an easier migratory reductive elimination of (sp(3))C-Rh-CO-C(sp(3)) by the introduction of CO. These reactions proceed in good yields for substrates with various tether types and substituents, providing a flexible, convenient, efficient, and stereocontrolled method for the construction of bicyclic cyclooctenones.