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. PMCID PMC6103296. doi:10.1021/jacs.8b05560. https://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:

URL	URL Type	Description
https://doi.org/10.1021/jacs.8b05560	DOI	Article
https://pubs.acs.org/doi/suppl/10.1021/jacs.8b05560	Publisher	Supporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6103296	PubMed Central	Article

ORCID:

Author	ORCID
Alexy, Eric J.	0000-0002-2971-9698
Zhang, Haiming	0000-0002-2139-2598
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 Agency	Grant Number
NIH	R01GM080269
Gordon and Betty Moore Foundation	UNSPECIFIED
Caltech	UNSPECIFIED
NSF Predoctoral Fellowship	UNSPECIFIED

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PubMed Central ID:

PMC6103296

DOI:

10.1021/jacs.8b05560

Record Number:

CaltechAUTHORS:20180727-091530074

Persistent URL:

https://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

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ID Code:

88319

Collection:

CaltechAUTHORS

Deposited By:

George Porter

Deposited On:

30 Jul 2018 14:33

Last Modified:

04 Mar 2022 17:01

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