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Access to Functionalized Quaternary Stereocenters via the Copper-Catalyzed Conjugate Addition of Monoorganozinc Bromide Reagents Enabled by N,N-Dimethylacetamide

Fulton, Tyler J. and Alley, Phebe L. and Rensch, Heather R. and Ackerman, Adriana M. and Berlin, Cameron B. and Krout, Michael R. (2018) Access to Functionalized Quaternary Stereocenters via the Copper-Catalyzed Conjugate Addition of Monoorganozinc Bromide Reagents Enabled by N,N-Dimethylacetamide. Journal of Organic Chemistry, 83 (23). pp. 14723-14732. ISSN 0022-3263. http://resolver.caltech.edu/CaltechAUTHORS:20181030-154210846

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Abstract

Monoorganozinc reagents, readily obtained from alkyl bromides, display excellent reactivity with β,β-disubstituted enones and TMSCl in the presence of Cu(I) and Cu(II) salts to synthesize a variety of cyclic functionalized β-quaternary ketones in 38–99% yields and 9:1–20:1 diastereoselectivities. The conjugate addition features a pronounced improvement in DMA using monoorganozinc bromide reagents. A simple one-pot protocol that harnesses in situ generated monoorganozinc reagents delivers comparable product yields.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.joc.8b02201DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/acs.joc.8b02201PublisherSupporting Information
ORCID:
AuthorORCID
Krout, Michael R.0000-0002-0539-6986
Additional Information:© 2018 American Chemical Society. Received: August 25, 2018; Published: October 30, 2018. The authors thank the American Chemical Society (ACS) Petroleum Research Fund Undergraduate New Investigator Program (Award No. 58488-UNI1), the ACS and Pfizer (research fellowship to T.J.F.), Bucknell University (research fellowships to H.R.R. and T.J.F.), and the Department of Chemistry (research fellowships to P.L.A, A.M.A., and C.B.B.) for generous support of this work. Dr. Peter M. Findeis and Brian Breczinski are acknowledged for experimental and instrumentation assistance. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
American Chemical Society Petroleum Research Fund58488-UNI1
PfizerUNSPECIFIED
Bucknell UniversityUNSPECIFIED
Record Number:CaltechAUTHORS:20181030-154210846
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20181030-154210846
Official Citation:Access to Functionalized Quaternary Stereocenters via the Copper-Catalyzed Conjugate Addition of Monoorganozinc Bromide Reagents Enabled by N,N-Dimethylacetamide. Tyler J. Fulton, Phebe L. Alley, Heather R. Rensch, Adriana M. Ackerman, Cameron B. Berlin, and Michael R. Krout. The Journal of Organic Chemistry 2018 83 (23), 14723-14732 DOI: 10.1021/acs.joc.8b02201
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:90528
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:30 Oct 2018 22:57
Last Modified:10 Dec 2018 19:32

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