Synthesis of Cyclopropenols Enabled by Visible‐Light‐Induced Organocatalyzed [2+1] Cyclization. (24th January 2022)

• Record Type: Journal Article
• Authors: Zhou, Gang; Shen, Xiao
• Is Part Of: Angewandte Chemie. Volume 134:Number 10(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-01-24
• Subjects: Cyclopropenol -- Energy Transfer Photocatalysis -- Homogeneous Catalysis -- Reaction Mechanisms -- Synthetic Methods; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202115334
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Although the synthesis of common cyclopropenes has been well studied, the access to cyclopropenols is rather limited. Herein, we report the first synthesis of α ‐ trifluoromethylated cyclopropenols via 2+1 cycloaddition reactions between alkynes and trifluoroacylsilanes, enabled by visible‐light‐induced organocatalysis. The novel ambiphilic donor–acceptor carbenes derived from trifluoroacetylsilanes reacted efficiently with both activated and non‐activated alkynes. The reaction features simple operation, mild conditions, broad substrate scope and good functional group tolerance. The synthetic potential of the reaction is highlighted by the gram‐scale reactions and first synthesis of α‐trifluoromethylated cyclopropanols through the combination of the 2+1 cyclization and high diastereoselective hydrogenation reaction in one pot. Abstract : An energy transfer photocatalysis strategy was developed for the synthesis of cyclopropenols. The novel donor–acceptor carbenes derived from trifluoroacetylsilanes reacted efficiently with both activated and non‐activated alkynes to form the 2+1 cyclization products. The synthetic potential of the reaction is highlighted by a gram‐scale reaction and the application in diastereoselective synthesis of trifluoromethylated cyclopropanols.