A Formal [3+3+1] Reaction of Enyne‐Methylenecyclopropanes through Au(I)‐Catalyzed Enyne Cycloisomerization and Rh(I)‐Catalyzed [6+1] Reaction of Vinylspiropentanes and CO. Issue 1 (22nd December 2021)

• Record Type: Journal Article
• Authors: Li, Chen‐Long; Yang, Yusheng; Zhou, Yi; Yu, Zhi‐Xiang
• Is Part Of: Asian journal of organic chemistry. Volume 11:Issue 1(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-12-22
• Subjects: gold -- enyne cycloisomerization -- rhodium -- [6+1] cycloaddition -- DFT calculations; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; 547.005
• DOI: 10.1002/ajoc.202100571
• Languages: English
• ISSNs: 2193-5807

Abstract

Abstract: A formal [3+3+1] reaction through gold(I)‐catalyzed enyne cycloisomerization of enyne‐methylenecyclopropanes and rhodium(I)‐catalyzed [6+1] reaction of vinylspiropentanes and CO has been developed to synthesize aza‐6/7 bicyclic compounds, hexahydrocyclohepta[ c ]pyridinones. DFT calculations reveal that four steps are involved in the [6+1] cycloaddition of vinylspiropentanes and CO, including oxidative addition of cyclopropane to Rh, β−C elimination, CO insertion and reductive elimination. Abstract : A formal [3+3+1] reaction of enyne‐methylenecyclopropanes and CO, which is combined by Au(I)‐catalyzed enyne cycloisomerization and Rh(I)‐catalyzed [6+1] reaction, has been developed to synthesize hexahydrocyclohepta[ c ]pyridinones. The 6c synthon in the [6+1] reaction is vinylspiropentanes, generated from Au‐catalyzed cycloisomerization of enyne‐methylenecyclopropanes. DFT study reveals that the [6+1] reaction starts from oxidative addition at the distal bond of non‐activated cyclopropane (rather than the proximal bond of activated cyclopropane with a vinyl substitution) in vinylspiropentanes, followed by β−C elimination, CO insertion and reductive elimination.