Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Cyclopentanones

[Image: see text] The first general method for the enantioselective construction of all-carbon quaternary centers on cyclopentanones by enantioselective palladium-catalyzed decarboxylative allylic alkylation is described. Employing the electronically modified (S)-(p-CF(3))(3)-t-BuPHOX ligand, α-quat...

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Autores principales: Craig, Robert A., Loskot, Steven A., Mohr, Justin T., Behenna, Douglas C., Harned, Andrew M., Stoltz, Brian M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2015
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4640231/
https://www.ncbi.nlm.nih.gov/pubmed/26501770
http://dx.doi.org/10.1021/acs.orglett.5b02376
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author Craig, Robert A.
Loskot, Steven A.
Mohr, Justin T.
Behenna, Douglas C.
Harned, Andrew M.
Stoltz, Brian M.
author_facet Craig, Robert A.
Loskot, Steven A.
Mohr, Justin T.
Behenna, Douglas C.
Harned, Andrew M.
Stoltz, Brian M.
author_sort Craig, Robert A.
collection PubMed
description [Image: see text] The first general method for the enantioselective construction of all-carbon quaternary centers on cyclopentanones by enantioselective palladium-catalyzed decarboxylative allylic alkylation is described. Employing the electronically modified (S)-(p-CF(3))(3)-t-BuPHOX ligand, α-quaternary cyclopentanones were isolated in yields up to >99% with ee’s up to 94%. Additionally, in order to facilitate large-scale application of this method, a low catalyst loading protocol was employed, using as little as 0.15 mol % Pd, furnishing the product without any loss in ee.
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spelling pubmed-46402312016-10-26 Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Cyclopentanones Craig, Robert A. Loskot, Steven A. Mohr, Justin T. Behenna, Douglas C. Harned, Andrew M. Stoltz, Brian M. Org Lett [Image: see text] The first general method for the enantioselective construction of all-carbon quaternary centers on cyclopentanones by enantioselective palladium-catalyzed decarboxylative allylic alkylation is described. Employing the electronically modified (S)-(p-CF(3))(3)-t-BuPHOX ligand, α-quaternary cyclopentanones were isolated in yields up to >99% with ee’s up to 94%. Additionally, in order to facilitate large-scale application of this method, a low catalyst loading protocol was employed, using as little as 0.15 mol % Pd, furnishing the product without any loss in ee. American Chemical Society 2015-10-26 2015-11-06 /pmc/articles/PMC4640231/ /pubmed/26501770 http://dx.doi.org/10.1021/acs.orglett.5b02376 Text en Copyright © 2015 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Craig, Robert A.
Loskot, Steven A.
Mohr, Justin T.
Behenna, Douglas C.
Harned, Andrew M.
Stoltz, Brian M.
Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Cyclopentanones
title Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Cyclopentanones
title_full Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Cyclopentanones
title_fullStr Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Cyclopentanones
title_full_unstemmed Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Cyclopentanones
title_short Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Cyclopentanones
title_sort palladium-catalyzed enantioselective decarboxylative allylic alkylation of cyclopentanones
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4640231/
https://www.ncbi.nlm.nih.gov/pubmed/26501770
http://dx.doi.org/10.1021/acs.orglett.5b02376
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