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Palladium-Catalyzed Decarbonylative Dehydration for the Synthesis of α-Vinyl Carbonyl Compounds and Total Synthesis of (−)-Aspewentins A, B, and C

Liu, Yiyang and Virgil, Scott C. and Grubbs, Robert H. and Stoltz, Brian M. (2015) Palladium-Catalyzed Decarbonylative Dehydration for the Synthesis of α-Vinyl Carbonyl Compounds and Total Synthesis of (−)-Aspewentins A, B, and C. Angewandte Chemie International Edition, 54 (40). pp. 11800-11803. ISSN 1433-7851. PMCID PMC4686263. http://resolver.caltech.edu/CaltechAUTHORS:20150807-083400322

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1002/anie.201505161DOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/anie.201505161/abstractPublisherArticle
http://onlinelibrary.wiley.com/doi/10.1002/anie.201505161/suppinfoPublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4686263/PubMed CentralArticle
ORCID:
AuthorORCID
Grubbs, Robert H.0000-0002-0057-7817
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Received: June 6, 2015. Article first published online: 29 July 2015. We wish to thank the Resnick Sustainability Institute at Caltech (graduate fellowship to Y.L.), NIH (R01M080269 to B.M.S., 5R01M031332-27 to R.H.G.), the Gordon and Betty Moore Foundation, the Caltech Center for Catalysis and Chemical Synthesis, and Caltech for financial support. Dr. David VanderVelde is acknowledged for assistance with NMR spectroscopy. Dr. Mona Shahgholi and Naseem Torian are acknowledged for assistance with high-resolution mass spectrometry. We would like to thank Prof. Richmond Sarpong of UC Berkeley for helpful discussions.
Group:Resnick Sustainability Institute
Funders:
Funding AgencyGrant Number
Resnick Sustainability InstituteUNSPECIFIED
NIHR01M080269-01
NIH5R01M031332-27
Gordon and Betty Moore FoundationUNSPECIFIED
CaltechUNSPECIFIED
Subject Keywords:enantioselectivity; natural products; olefination; palladium; total synthesis
PubMed Central ID:PMC4686263
Record Number:CaltechAUTHORS:20150807-083400322
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150807-083400322
Official Citation:Liu, Y., Virgil, S. C., Grubbs, R. H. and Stoltz, B. M. (2015), Palladium-Catalyzed Decarbonylative Dehydration for the Synthesis of α-Vinyl Carbonyl Compounds and Total Synthesis of (−)-Aspewentins A, B, and C. Angew. Chem. Int. Ed., 54: 11800–11803. doi:10.1002/anie.201505161
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59300
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:07 Aug 2015 15:58
Last Modified:19 Jul 2017 20:34

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