CaltechAUTHORS
  A Caltech Library Service

Enantioselective Construction of Acyclic Quaternary Carbon Stereocen-ters: 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 Stereocen-ters: 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. https://resolver.caltech.edu/CaltechAUTHORS:20170623-095559709

[img] PDF - Accepted Version
See Usage Policy.

12Mb
[img] PDF (Experimental procedures and characterization data) - Supplemental Material
See Usage Policy.

15Mb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20170623-095559709

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:
URLURL TypeDescription
http://dx.doi.org/10.1021/jacs.7b04086DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jacs.7b04086PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jacs.7b04086PublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5555155/PubMed CentralArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5555155/#PubMed CentralSupporting Information
ORCID:
AuthorORCID
Starkov, Pavel0000-0003-1421-4731
Stoltz, Brian M.0000-0001-9837-1528
Marek, Ilan0000-0001-9154-2320
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 AgencyGrant Number
Israel Science FoundationUNSPECIFIED
Israel Academy of Sciences and Humanities140/12
TechnionUNSPECIFIED
NIHR01GM080269
NSF Graduate Research FellowshipDGE-1144469
NIH Postdoctoral FellowshipF32GM116304
Issue or Number:28
PubMed Central ID:PMC5555155
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
Usage Policy: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:03 Oct 2019 18:09

Repository Staff Only: item control page