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Catalytic Enantioselective Synthesis of Acyclic Quaternary Centers: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Acyclic Enol Carbonates

Alexy, Eric J. and Zhang, Haiming and Stoltz, Brian M. (2018) Catalytic Enantioselective Synthesis of Acyclic Quaternary Centers: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Acyclic Enol Carbonates. Journal of the American Chemical Society, 140 (32). pp. 10109-10112. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20180727-091530074

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Abstract

The first enantioselective palladium-catalyzed decarboxylative allylic alkylation of fully substituted acyclic enol carbonates providing linear α-quaternary ketones is reported. Investigation into the reaction revealed that the use of an electron-deficient phosphinooxazoline ligand renders the enolate geometry of the starting material inconsequential, with the same enantiomer of product obtained in the same level of selectivity regardless of the starting ratio of enolates. As a result, a general method toward acyclic all-carbon quaternary stereocenters has been developed.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.8b05560DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/jacs.8b05560PublisherSupporting Information
ORCID:
AuthorORCID
Zhang, Haiming0000-0002-2139-2598
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2018 American Chemical Society. Received: May 27, 2018; Published: July 26, 2018. We thank NIH-NIGMS (R01GM080269), the Gordon and Betty Moore Foundation, and Caltech for financial support. E.J.A. thanks the National Science Foundation for a predoctoral fellowship. We thank Dr. David VanderVelde (Caltech) for NMR expertise. Dr. Scott Virgil (Caltech) is thanked for instrumentation and SFC assistance. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NIHR01GM080269
Gordon and Betty Moore FoundationUNSPECIFIED
CaltechUNSPECIFIED
NSF Predoctoral FellowshipUNSPECIFIED
Record Number:CaltechAUTHORS:20180727-091530074
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180727-091530074
Official Citation:Catalytic Enantioselective Synthesis of Acyclic Quaternary Centers: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Acyclic Enol Carbonates. Eric J. Alexy, Haiming Zhang, and Brian M. Stoltz. Journal of the American Chemical Society 2018 140 (32), 10109-10112. DOI: 10.1021/jacs.8b05560
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:88319
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:30 Jul 2018 14:33
Last Modified:20 Aug 2018 21:17

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