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Enantioselective synthesis of highly oxygenated acyclic quaternary center-containing building blocks via palladium-catalyzed decarboxylative allylic alkylation of cyclic siloxyketones

Ngamnithiporn, Aurapat and Iwayama, Toshihiko and Bartberger, Michael D. and Stoltz, Brian M. (2020) Enantioselective synthesis of highly oxygenated acyclic quaternary center-containing building blocks via palladium-catalyzed decarboxylative allylic alkylation of cyclic siloxyketones. Chemical Science, 11 (40). pp. 11068-11071. ISSN 2041-6520. https://resolver.caltech.edu/CaltechAUTHORS:20200925-104734427

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Abstract

The development of a palladium-catalyzed enantioselective decarboxylative allylic alkylation of cyclic siloxyketones to produce enantioenriched silicon-tethered heterocycles is reported. The reaction proceeds smoothly to provide products bearing a quaternary stereocenter in excellent yields (up to 91% yield) with high levels of enantioselectivity (up to 94% ee). We further utilized the unique reactivity of the siloxy functionality to access chiral, highly oxygenated acyclic quaternary building blocks. In addition, we subsequently demonstrated the utility of these compounds through the synthesis of a lactone bearing vicinal quaternary-trisubstituted stereocenters.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1039/d0sc04383dDOIArticle
ORCID:
AuthorORCID
Ngamnithiporn, Aurapat0000-0002-5389-8171
Bartberger, Michael D.0000-0002-5167-3139
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:This journal is © The Royal Society of Chemistry 2020. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Received 9th August 2020. Accepted 10th September 2020. The NIH-NIGMS (R01GM080269) and Caltech are thanked for support of our research program. A. N. thanks the Royal Thai Government Scholarship program. T. I. thanks Japan Tobacco Inc. for funding. We thank Dr Makoto Shiozaki for helpful discussion and Dr Mona Shahgholi for mass spectrometry assistant. Dr Scott Virgil is acknowledged for instrumentation and SFC assistance. A. N. and T. I. contributed equally to this work. All publication charges for this article have been paid for by the Royal Society of Chemistry.
Funders:
Funding AgencyGrant Number
NIHR01GM080269
CaltechUNSPECIFIED
Royal Thai Government Scholarship ProgramUNSPECIFIED
Japan Tobacco Inc.UNSPECIFIED
Royal Society of ChemistryUNSPECIFIED
Issue or Number:40
Record Number:CaltechAUTHORS:20200925-104734427
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200925-104734427
Official Citation:Enantioselective synthesis of highly oxygenated acyclic quaternary center-containing building blocks via palladium-catalyzed decarboxylative allylic alkylation of cyclic siloxyketones. Chem. Sci., 2020, 11, 11068-11071; doi: 10.1039/d0sc04383d
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:105551
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:25 Sep 2020 20:06
Last Modified:22 Oct 2020 16:07

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