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Enantioselective Pd-Catalyzed Decarboxylative Allylic Alkylation of Thiopyranones. Access to Acyclic, Stereogenic α-Quaternary Ketones

Alexy, Eric J. and Virgil, Scott C. and Bartberger, Michael D. and Stoltz, Brian M. (2017) Enantioselective Pd-Catalyzed Decarboxylative Allylic Alkylation of Thiopyranones. Access to Acyclic, Stereogenic α-Quaternary Ketones. Organic Letters, 19 (19). pp. 5007-5009. ISSN 1523-7060. https://resolver.caltech.edu/CaltechAUTHORS:20170914-131404458

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Abstract

A catalytic, enantioselective decarboxylative allylic alkylation of 4-thiopyranones is reported. The α-quaternary 4-thiopyranones produced are challenging to access by standard enolate alkylation owing to facile ring-opening β-sulfur elimination. In addition, reduction of the carbon–sulfur bonds provides access to elusive acyclic α-quaternary ketones. The alkylated products are obtained in up to 92% yield and 94% enantiomeric excess.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.orglett.7b02354DOIArticle
http://pubs.acs.org/doi/abs/10.1021/acs.orglett.7b02354PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acs.orglett.7b02354PublisherSupporting Information
ORCID:
AuthorORCID
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2017 American Chemical Society. Received: July 30, 2017; Published: September 13, 2017. We thank NIH-NIGMS (R01GM080269), Amgen, the Gordon and Betty Moore Foundation, and Caltech for financial support. E.J.A. is grateful to the National Science Foundation for a predoctoral fellowship. We thank Dr. David VanderVelde (Caltech) for NMR expertise, and Dr. Mona Shahgholi (Caltech) and Naseem Torian (Caltech) for mass spectrometry assistance. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NIHR01GM080269
AmgenUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
CaltechUNSPECIFIED
NSF Predoctoral FellowshipUNSPECIFIED
Issue or Number:19
Record Number:CaltechAUTHORS:20170914-131404458
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170914-131404458
Official Citation:Enantioselective Pd-Catalyzed Decarboxylative Allylic Alkylation of Thiopyranones. Access to Acyclic, Stereogenic α-Quaternary Ketones Eric J. Alexy, Scott C. Virgil, Michael D. Bartberger, and Brian M. Stoltz Organic Letters 2017 19 (19), 5007-5009 DOI: 10.1021/acs.orglett.7b02354
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:81444
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:14 Sep 2017 21:58
Last Modified:03 Oct 2019 18:42

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