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Enantioselective synthesis of gem-disubstituted N-Boc diazaheterocycles via decarboxylative asymmetric allylic alkylation

Sun, Alexander W. and Hess, Stephan N. and Stoltz, Brian M. (2019) Enantioselective synthesis of gem-disubstituted N-Boc diazaheterocycles via decarboxylative asymmetric allylic alkylation. Chemical Science, 10 (3). pp. 788-792. ISSN 2041-6520. PMCID PMC6345351. https://resolver.caltech.edu/CaltechAUTHORS:20181106-111914131

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Abstract

An enantioselective synthesis of diverse N4-Boc-protected α,α-disubstituted piperazin-2-ones using the palladium-catalyzed decarboxylative allylic alkylation reaction has been achieved. Using a chiral Pd-catalyst derived from an electron deficient PHOX ligand, chiral piperazinones are synthesized in high yields and enantioselectivity. The chiral piperazinone products can be deprotected and reduced to valuable gem-disubstituted piperazines. This reaction is further extended to enable the enantioselective synthesis of α,α-disubstituted tetrahydropyrimidin-2-ones, which are hydrolyzed into corresponding chiral β^(2,2)-amino acids.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1039/c8sc03967dDOIArticle
http://www.rsc.org/suppdata/c8/sc/c8sc03967d/c8sc03967d1.pdfPublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6345351PubMed CentralArticle
http://resolver.caltech.edu/CaltechAUTHORS:20190325-092717158Related ItemConference Paper
ORCID:
AuthorORCID
Sun, Alexander W.0000-0001-6639-4469
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2018 The Royal Society of Chemistry. Open Access Article. Published on 31 October 2018. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. All publication charges for this article have been paid for by the Royal Society of Chemistry. The article was received on 06 Sep 2018, accepted on 29 Oct 2018 and first published on 31 Oct 2018. The NIH-NIGMS (R01GM080269) and Caltech are thanked for support of our research program. Additionally, A. W. S. thanks the NIH-NIGMS for a predoctoral fellowship (Ruth L. Kirschstein Institutional National Research Service Award F30GM120836) and a UCLA-Caltech Medical Scientist Training Program Fellowship (T32GM008042). S. N. H. thanks the Bayer Foundation for an Otto Bayer Scholarship. Dr David VanderVelde is thanked for assistance with structural assignments via NMR analysis. Dr Scott Virgil, Dr Marchello Cavitt, Dr Brendan O'Boyle, Dr Justin Hilf, Dr Corey Reeves, and Kevin Yang are thanked for helpful discussions.
Funders:
Funding AgencyGrant Number
NIHR01GM080269
CaltechUNSPECIFIED
NIH Postdoctoral FellowshipF30GM120836
NIH Predoctoral FellowshipT32GM008042
Bayer FoundationUNSPECIFIED
UCLA-Caltech Medical Scientist Training ProgramUNSPECIFIED
Issue or Number:3
PubMed Central ID:PMC6345351
Record Number:CaltechAUTHORS:20181106-111914131
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20181106-111914131
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:90670
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:06 Nov 2018 21:58
Last Modified:03 Oct 2019 20:27

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