Gold Self-Relay Catalysis Enabling [3,3]-Sigmatropic Rearrangement/Nazarov Cyclization and Allylic Alkylation Cascade for Constructing All-Carbon Quaternary Stereocenters

Fan-Tao Meng, Xiao-Yan Qin, Jing Li, Tian-Shu Zhang,* Shu-Jiang Tu, Bo Jiang,* Wen-Juan Hao*,

Molecular scaffolds endowed with all-carbon quaternary stereocenter are ubiquitous in natural products and significant bioactive molecules. However, efficient construction of this type of structure units is full of challenge due to its congested chemical environment. Herein, we report a new gold(I) self-relay catalysis merging [3,3]-sigmatropic rearrangement/Nazarov cyclization with allylic alkylation starting from 1,3-enyne acetates and allylic alcohols, producing a wide range of synthetically important allyl cyclopentenones with an all-carbon quaternary stereocenter in good yields under the mild conditions. This protocol demonstrates the precise control of regioselectivity, high functional group tolerance of substrates and the low loading of gold catalyst without inert atmosphere protection, providing a catalytic and efficient entry to all-carbon quaternary stereocenters.

Chin. J. Chem. 2022, 40, 687-692; DOI: 10.1002/cjoc.202100734