A Desulfonylative Approach in Oxidative Gold Catalysis: Regiospecific Access to Donor‐Substituted Acyl Gold Carbenes. Issue 40 (12th August 2015)

• Record Type: Journal Article
• Authors: Chen, Hongyi; Zhang, Liming
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 40(2015)
• Page Start: 11775
• Page End: 11779
• Publication Date: 2015-08-12
• Subjects: carbenes -- gold -- oxidation -- sulfur -- synthetic methods; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201504511
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Donor‐substituted acyl gold carbenes are challenging to access selectively by gold‐promoted intermolecular oxidation of internal alkynes as the opposite regioisomers frequently predominate. By using alkynyl sulfones or sulfonates as substrates, the oxidative gold catalysis in the presence of substituted pyridine N ‐oxides offers regiospecific access to acyl/aryl, acyl/alkenyl, and acyl/alkoxy gold carbenes by in situ expulsion of sulfur dioxide. The intermediacies of these reactive species are established by their reactivities, including undergoing further oxidation by the same oxidant, cyclopropanation of styrenes, engaging in a [3+2] cycloaddition with α‐methylstyrene, and conversion into dienones. Abstract : Accept it : A desulfonylative approach was developed to regiospecifically access these underexplored acyl gold carbenes from either alkynyl aryl/alkenyl sulfones or alkynyl sulfonate substrates. The reactivities of these donor‐ and acceptor‐substituted carbenes are examined.