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. PMCID PMC5632216. doi:10.1021/acs.orglett.7b02354. 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:

URL	URL Type	Description
https://doi.org/10.1021/acs.orglett.7b02354	DOI	Article
https://pubs.acs.org/doi/suppl/10.1021/acs.orglett.7b02354	Publisher	Supporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5632216	PubMed Central	Article

ORCID:

Author	ORCID
Alexy, Eric J.	0000-0002-2971-9698
Virgil, Scott C.	0000-0001-8586-5641
Bartberger, Michael D.	0000-0002-5167-3139
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 Agency	Grant Number
NIH	R01GM080269
Amgen	UNSPECIFIED
Gordon and Betty Moore Foundation	UNSPECIFIED
Caltech	UNSPECIFIED
NSF Predoctoral Fellowship	UNSPECIFIED

Issue or Number:

PubMed Central ID:

PMC5632216

DOI:

10.1021/acs.orglett.7b02354

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

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ID Code:

81444

Collection:

CaltechAUTHORS

Deposited By:

Tony Diaz

Deposited On:

14 Sep 2017 21:58

Last Modified:

22 Mar 2022 19:25

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