Palladium‐Catalyzed Cascade Carbonylation to α, β‐Unsaturated Piperidones via Selective Cleavage of Carbon–Carbon Triple Bonds. Issue 41 (6th September 2021)

• Record Type: Journal Article
• Authors: Ge, Yao; Ye, Fei; Yang, Ji; Spannenberg, Anke; Jiao, Haijun; Jackstell, Ralf; Beller, Matthias
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 41(2021)
• Page Start: 22393
• Page End: 22400
• Publication Date: 2021-09-06
• Subjects: bond cleavage -- cascade carbonylation -- homogeneous catalysis -- palladium -- α, β-unsaturated piperidones; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202108120
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A direct and selective synthesis of α, β‐unsaturated piperidones by a new palladium‐catalyzed cascade carbonylation is described. In the presented protocol, easily available propargylic alcohols react with aliphatic amines to provide a broad variety of interesting heterocycles. Key to the success of this transformation is a remarkable catalytic cleavage of the present carbon–carbon triple bond by using a specific catalyst with 2‐diphenylphosphinopyridine as ligand and appropriate reaction conditions. Mechanistic studies and control experiments revealed branched unsaturated acid 11 as crucial intermediate. Abstract : A catalytic carbonylative cleavage of carbon–carbon triple bonds is achieved. This allows for a general and direct synthesis of α, β‐unsaturated piperidones by palladium‐catalyzed cascade carbonylation of alkynols.