An Exclusively trans‐Selective Chlorocarbamoylation of Alkynes Enabled by a Palladium/Phosphaadamantane Catalyst. Issue 52 (20th November 2015)

• Record Type: Journal Article
• Authors: Le, Christine M.; Hou, Xiao; Sperger, Theresa; Schoenebeck, Franziska; Lautens, Mark
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 52(2015)
• Page Start: 15897
• Page End: 15900
• Publication Date: 2015-11-20
• Subjects: chlorocarbamoylation -- cyclization -- homogenous catalysis -- palladium -- phosphaadamantane; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201507883
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Pharmaceutically relevant methylene oxindoles are synthesized by a palladium(0)‐catalyzed intramolecular chlorocarbamoylation reaction of alkynes. A relatively underexplored class of caged phosphine ligands is uniquely suited for this transformation, enabling high levels of reactivity and exquisite trans selectivity. This report entails the first transition‐metal‐catalyzed atom‐economic addition of a carbamoyl chloride across an alkyne. Abstract : A new ­ trans ‐formation : The use of bulky, electron‐deficient phosphaadamantane ligands in combination with sterically hindered alkynes enabled a palladium(0)‐catalyzed alkyne chlorocarbamoylation reaction with high reactivity and exclusive trans selectivity.