CaltechAUTHORS
  A Caltech Library Service

Copper-Catalyzed Enantioselective Allylic Alkylation with a γ-Butyrolactone-Derived Silyl Ketene Acetal

Jette, Carina I. and Tong, Z. Jaron and Hadt, Ryan G. and Stoltz, Brian M. (2020) Copper-Catalyzed Enantioselective Allylic Alkylation with a γ-Butyrolactone-Derived Silyl Ketene Acetal. Angewandte Chemie International Edition, 59 (5). pp. 2033-2038. ISSN 1433-7851. PMCID PMC7051182 . https://resolver.caltech.edu/CaltechAUTHORS:20191120-075819004

[img] PDF - Accepted Version
See Usage Policy.

1218Kb
[img] PDF - Supplemental Material
See Usage Policy.

17Mb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20191120-075819004

Abstract

Herein, we report a Cu‐catalyzed enantioselective allylic alkylation using a γ‐butyrolactone‐derived silyl ketene acetal. Critical to the development of this work was the identification of a novel mono‐picolinamide ligand with the appropriate steric and electronic properties to afford the desired products in high yield (up to 96 %) and high ee (up to 95 %). Aryl, aliphatic, and unsubstituted allylic chlorides bearing a broad range of functionality are well‐tolerated. Spectroscopic studies reveal that a Cu^I species is likely the active catalyst, and DFT calculations suggest ligand sterics play an important role in determining Cu coordination and thus catalyst geometry.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1002/anie.201912618DOIArticle
http://www.ncbi.nlm.nih.gov/pmc/articles/pmc7051182/PubMed CentralArticle
ORCID:
AuthorORCID
Jette, Carina I.0000-0002-8476-6032
Tong, Z. Jaron0000-0001-9329-8034
Hadt, Ryan G.0000-0001-6026-1358
Stoltz, Brian M.0000-0001-9837-1528
Alternate Title:Cu-Catalyzed Enantioselective Allylic Alkylation with a γ-Butyrolactone-Derived Silyl Ketene Acetal
Additional Information:© 2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim. Issue Online: 24 January 2020; Version of Record online: 16 December 2019; Accepted manuscript online: 19 November 2019; Manuscript revised: 12 November 2019; Manuscript received: 06 October 2019. The NIH‐NIGMS (R01GM080269) and Caltech are thanked for support of our research program. Financial support from Caltech and the Dow Next Generation Educator Fund is gratefully acknowledged (R.G.H.). C.I.J. thanks the National Science Foundation for a predoctoral fellowship. Alexander Q. Cusumano is thanked for assistance and helpful discussions, Dr. Scott Virgil for instrumentation and SFC assistance, Lawrence Henling for assistance with X‐Ray analysis, Dr. Mona Shahgholi for mass spectrometry assistance, Dr. Paul H. Oyala for his assistance with EPR spectroscopy, and Prof. H. B. Gray for the use of the Cary 500 UV‐vis‐NIR spectrophotometer. The authors declare no conflict of interest.
Funders:
Funding AgencyGrant Number
NIHR01GM080269
CaltechUNSPECIFIED
Dow Next Generation Educator FundUNSPECIFIED
NSF Predoctoral FellowshipUNSPECIFIED
Subject Keywords:allylic alkylation; asymmetric catalysis; copper; enolate nucleophiles; γ-butyrolactones
Issue or Number:5
PubMed Central ID:PMC7051182
Record Number:CaltechAUTHORS:20191120-075819004
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20191120-075819004
Official Citation:Copper-Catalyzed Enantioselective Allylic Alkylation with a γ-Butyrolactone-Derived Silyl Ketene Acetal. C. I. Jette, Z. J. Tong, R. G. Hadt, B. M. Stoltz, Angew. Chem. Int. Ed. 2020, 59, 2033; doi: 10.1002/anie.201912618
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:99942
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:20 Nov 2019 19:15
Last Modified:10 Apr 2020 18:38

Repository Staff Only: item control page