CaltechAUTHORS
  A Caltech Library Service

Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement

Liu, Wen-Bo and Okamoto, Noriko and Alexy, Eric J. and Hong, Allen Y. and Tran, Kristy and Stoltz, Brian M. (2016) Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement. Journal of the American Chemical Society, 138 (16). pp. 5234-5237. ISSN 0002-7863. PMCID PMC5497580. http://resolver.caltech.edu/CaltechAUTHORS:20160427-092037065

[img] PDF - Accepted Version
See Usage Policy.

1766Kb
[img] PDF (Experimental procedures and characterization data) - Supplemental Material
See Usage Policy.

3210Kb
[img] PDF (1H NMR and 13C NMR spectra) - Supplemental Material
See Usage Policy.

3767Kb
[img] Crystallographic Info File (CIF) (Single crystal X-ray analysis) - Supplemental Material
See Usage Policy.

801Kb
[img] Crystallographic Info File (CIF) (Single crystal X-ray analysis) - Supplemental Material
See Usage Policy.

878Kb

Use this Persistent URL to link to this item: http://resolver.caltech.edu/CaltechAUTHORS:20160427-092037065

Abstract

A catalytic, enantioselective γ-alkylation of α,β-unsaturated malonates and ketoesters is reported. This strategy entails a highly regio- and enantioselective iridium-catalyzed α-alkylation of an extended enolate, and a subsequent translocation of chirality to the γ-position via a Cope rearrangement.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jacs.6b02153DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jacs.6b02153PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jacs.6b02153PublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5497580PubMed CentralArticle
ORCID:
AuthorORCID
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2016 American Chemical Society. Received: February 26, 2016. Published: April 7, 2016. We thank NIH-NIGMS (R01GM080269), the Gordon and Betty Moore Foundation, and Caltech for financial support. Shanghai Institute of Organic Chemistry (SIOC) is thanked for a postdoctoral fellowship to W.-B.L. Hiroshima International University is thanked for a postdoctoral fellowship to N.O. E.J.A. is grateful to the National Science Foundation for a predoctoral fellowship. K.T. acknowledges support from California HIV/AIDS Research Program (F08-CT-201). Mr. Lawrence Henlingand Dr. Michael Takase are acknowledged for X-ray analyses. We thank Dr. David VanderVelde for NMR expertise, and Dr. Mona Shahgholi and Naseem Torian for mass spectrometry assistance. The authors are also thankful to Professor Shu-Li You for the generous donation of N-aryl ligands and for helpful discussions.
Funders:
Funding AgencyGrant Number
NIHR01GM080269
Gordon and Betty Moore FoundationUNSPECIFIED
CaltechUNSPECIFIED
Shanghai Institute of Organic Chemistry (SIOC)UNSPECIFIED
Hiroshima International UniversityUNSPECIFIED
NSFUNSPECIFIED
California HIV/AIDS Research ProgramF08-CT-201
PubMed Central ID:PMC5497580
Record Number:CaltechAUTHORS:20160427-092037065
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20160427-092037065
Official Citation:Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement Wen-Bo Liu, Noriko Okamoto, Eric J. Alexy, Allen Y. Hong, Kristy Tran, and Brian M. Stoltz Journal of the American Chemical Society 2016 138 (16), 5234-5237 DOI: 10.1021/jacs.6b02153
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:66506
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:27 Apr 2016 17:52
Last Modified:17 Jul 2017 22:39

Repository Staff Only: item control page