A new gold(I)self-relay catalysis consisting of a 3,3-rearrangement,Nazarov cyclization and Michael addition cascade of 1,3-enyne acetates with aurones and their derived azadienes is reported,and used to produce a ser...A new gold(I)self-relay catalysis consisting of a 3,3-rearrangement,Nazarov cyclization and Michael addition cascade of 1,3-enyne acetates with aurones and their derived azadienes is reported,and used to produce a series of densely functionalized cyclopentenones bearing a cyclic quaternary stereocenter in moderate to good yields under mild conditions.This tandem protocol demonstrates high regioselectivity,broad substrate flexibility and good functional group tolerance of substrates without inert atmosphere protection,providing a catalytic and convergent approach for creating all-carbon stereoscopic centers.展开更多
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 chal...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.展开更多
基金the National Natural Science Foundation of China(no.21971090)the Top-Notch Academic Programs Project of Jiangsu Higher Education Institution(TAPP).
文摘A new gold(I)self-relay catalysis consisting of a 3,3-rearrangement,Nazarov cyclization and Michael addition cascade of 1,3-enyne acetates with aurones and their derived azadienes is reported,and used to produce a series of densely functionalized cyclopentenones bearing a cyclic quaternary stereocenter in moderate to good yields under mild conditions.This tandem protocol demonstrates high regioselectivity,broad substrate flexibility and good functional group tolerance of substrates without inert atmosphere protection,providing a catalytic and convergent approach for creating all-carbon stereoscopic centers.
基金We are grateful for financial support from the National Natural Science Foundation of China(Nos.21871112 and 21971090)the Science and Technology of Xuzhou(KC21022)。
文摘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.
