Enantioselective Construction of Acyclic Quaternary Carbon Stereocenters: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully-Substituted Amide Enolates

Starkov, Pavel and Moore, Jared T. and Duquette, Douglas C. and Stoltz, Brian M. and Marek, Ilan (2017) Enantioselective Construction of Acyclic Quaternary Carbon Stereocenters: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully-Substituted Amide Enolates. Journal of the American Chemical Society, 139 (28). pp. 9615-9620. ISSN 0002-7863. PMCID PMC5555155. doi:10.1021/jacs.7b04086. https://resolver.caltech.edu/CaltechAUTHORS:20170623-095559709

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Abstract

We report a divergent and modular protocol for the preparation of acyclic molecular frameworks containing newly created quaternary carbon stereocenters. Central to this approach is a sequence composed of a (1) regioselective and -retentive preparation of allyloxycarbonyl-trapped fully substituted stereodefined amide enolates and of a (2) enantioselective palladium-catalyzed decarboxylative allylic alkylation reaction using a novel bisphosphine ligand.

Item Type:

Article

Related URLs:

URL	URL Type	Description
https://doi.org/10.1021/jacs.7b04086	DOI	Article
https://pubs.acs.org/doi/suppl/10.1021/jacs.7b04086	Publisher	Supporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5555155	PubMed Central	Article

ORCID:

Author	ORCID
Starkov, Pavel	0000-0003-1421-4731
Stoltz, Brian M.	0000-0001-9837-1528
Marek, Ilan	0000-0001-9154-2320

Additional Information:

© 2017 American Chemical Society. Received: April 22, 2017; Published: June 19, 2017. This research was supported by the Israel Science Foundation administrated by the Israel Academy of Sciences and Humanities (140/12), the Fund for Promotion of Research at the Technion, the NIH-NIGMS (R01GM080269), and the NSF (predoctoral research fellowship to D.C.D., No. DGE-1144469). Research reported in this publication was supported by the NIH-NIGMS under Award Number F32GM116304 (postdoctoral fellowship to J.T.M.). I.M. is holder of the Sir Michael and Lady Sobell Academic Chair (Technion). Dr. Mona Shahgholi (Caltech) and Naseem Torian (Caltech) are thanked for mass spectrometry assistance. Dr. Scott Virgil (Caltech) is thanked for instrumentation assistance and helpful discussions. The authors declare no competing financial interest.

Funders:

Funding Agency	Grant Number
Israel Science Foundation	UNSPECIFIED
Israel Academy of Sciences and Humanities	140/12
Technion	UNSPECIFIED
NIH	R01GM080269
NSF Graduate Research Fellowship	DGE-1144469
NIH Postdoctoral Fellowship	F32GM116304

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PubMed Central ID:

PMC5555155

DOI:

10.1021/jacs.7b04086

Record Number:

CaltechAUTHORS:20170623-095559709

Persistent URL:

https://resolver.caltech.edu/CaltechAUTHORS:20170623-095559709

Official Citation:

Enantioselective Construction of Acyclic Quaternary Carbon Stereocenters: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Amide Enolates Pavel Starkov, Jared T. Moore, Douglas C. Duquette, Brian M. Stoltz, and Ilan Marek Journal of the American Chemical Society 2017 139 (28), 9615-9620 DOI: 10.1021/jacs.7b04086

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No commercial reproduction, distribution, display or performance rights in this work are provided.

ID Code:

78510

Collection:

CaltechAUTHORS

Deposited By:

Tony Diaz

Deposited On:

24 Jun 2017 03:08

Last Modified:

23 Mar 2022 20:36

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