Palladium‐Catalyzed Decarbonylative Dehydration for the Synthesis of α‐Vinyl Carbonyl Compounds and Total Synthesis of (−)‐Aspewentins A,B, and C |
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| Authors: | Yiyang Liu Dr. Scott C. Virgil Prof. Robert H. Grubbs Prof. Brian M. Stoltz |
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| Affiliation: | The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd, MC 101‐20, Pasadena, CA 91125 (USA) |
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| Abstract: | The direct α‐vinylation of carbonyl compounds to form a quaternary stereocenter is a challenging transformation. It was discovered that δ‐oxocarboxylic acids can serve as masked vinyl compounds and be unveiled by palladium‐catalyzed decarbonylative dehydration. The carboxylic acids are readily available through enantioselective acrylate addition or asymmetric allylic alkylation. A variety of α‐vinyl quaternary carbonyl compounds are obtained in good yields, and an application in the first enantioselective total synthesis of (?)‐aspewentins A, B, and C is demonstrated. |
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| Keywords: | enantioselectivity natural products olefination palladium total synthesis |
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