Conjugated polyene motifs are ubiquitous in various natural products and functional molecules;however,their synthesis is very challenging because of the required lengthy and time-consuming processes.We herein report a...Conjugated polyene motifs are ubiquitous in various natural products and functional molecules;however,their synthesis is very challenging because of the required lengthy and time-consuming processes.We herein report an efficient approach for the synthesis of(E,E)-trienes via cationic rhodium catalysis using acetylene and simple alkenes bearing diverse directing groups as the starting materials.The reaction featured high step economy,excellent functional group compatibility,and exclusive stereoselectivity.Various directing groups such as carbonyl,sulfone,phosphate,hydroxyl,and amino were compatible.Furthermore,the triene products allowed versatile elaborations,providing rapid and convenient access to several important bioactive molecules,including vitamin A,(+)-roxaticin,and other complex polyenes.Mechanistic experiments showed that the directing group on the alkene played a crucial role in the reaction.展开更多
基金the NSFC(grant nos.21871096,22071062,22271096),and the Fundamental Research Funds for the Central Universities,SCUT.
文摘Conjugated polyene motifs are ubiquitous in various natural products and functional molecules;however,their synthesis is very challenging because of the required lengthy and time-consuming processes.We herein report an efficient approach for the synthesis of(E,E)-trienes via cationic rhodium catalysis using acetylene and simple alkenes bearing diverse directing groups as the starting materials.The reaction featured high step economy,excellent functional group compatibility,and exclusive stereoselectivity.Various directing groups such as carbonyl,sulfone,phosphate,hydroxyl,and amino were compatible.Furthermore,the triene products allowed versatile elaborations,providing rapid and convenient access to several important bioactive molecules,including vitamin A,(+)-roxaticin,and other complex polyenes.Mechanistic experiments showed that the directing group on the alkene played a crucial role in the reaction.
