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

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 their congested chemical envi-ronment.Herein,we report a new gold(Ⅰ)self-relay catalysis merging[3,3]-sigmatropic rearrangement/Nazarov cyclization with al-lylic alkylation starting from 1,3-enyne acetates and allylic alcohols,producing a wide range of synthetically important allyl cyclo-pentenones with an all-carbon quaternary stereocenter in good yields under 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 atmos-phere protection,providing a catalytic and efficient entry to all-carbon quaternary stereocenters.