Directing the Stereoselectivity of the Claisen Rearrangement to Form Cyclic Ketones with Full Substitution at the α-Positions

[Image: see text] We report an enantioselective synthesis of cyclic ketones with full substitutions at the α-positions in a highly diastereoselective manner. Our method is achieved by subjecting substrate motifs in 2-allyloxyenones to chiral organomagnesium reagents, which trigger the Claisen rearra...

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Autores principales: Badmus, Fatimat O., Thombal, Raju S., Philkhana, Satish Chandra, Malone, Joshua A., Bailey, Christian E., Armendariz-Gonzalez, Estefania, Mureka, Edward W., Locicero, Cale M., Fronczek, Frank R., Kartika, Rendy
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10616857/
https://www.ncbi.nlm.nih.gov/pubmed/37830497
http://dx.doi.org/10.1021/acs.orglett.3c02752
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author Badmus, Fatimat O.
Thombal, Raju S.
Philkhana, Satish Chandra
Malone, Joshua A.
Bailey, Christian E.
Armendariz-Gonzalez, Estefania
Mureka, Edward W.
Locicero, Cale M.
Fronczek, Frank R.
Kartika, Rendy
author_facet Badmus, Fatimat O.
Thombal, Raju S.
Philkhana, Satish Chandra
Malone, Joshua A.
Bailey, Christian E.
Armendariz-Gonzalez, Estefania
Mureka, Edward W.
Locicero, Cale M.
Fronczek, Frank R.
Kartika, Rendy
author_sort Badmus, Fatimat O.
collection PubMed
description [Image: see text] We report an enantioselective synthesis of cyclic ketones with full substitutions at the α-positions in a highly diastereoselective manner. Our method is achieved by subjecting substrate motifs in 2-allyloxyenones to chiral organomagnesium reagents, which trigger the Claisen rearrangement upon direct 1,2-carbonyl addition. The observed diastereoselectivity of the allyl migration is proposed to originate from the intramolecular chelation of the magnesium alkoxide to the allyloxy moiety.
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spelling pubmed-106168572023-11-01 Directing the Stereoselectivity of the Claisen Rearrangement to Form Cyclic Ketones with Full Substitution at the α-Positions Badmus, Fatimat O. Thombal, Raju S. Philkhana, Satish Chandra Malone, Joshua A. Bailey, Christian E. Armendariz-Gonzalez, Estefania Mureka, Edward W. Locicero, Cale M. Fronczek, Frank R. Kartika, Rendy Org Lett [Image: see text] We report an enantioselective synthesis of cyclic ketones with full substitutions at the α-positions in a highly diastereoselective manner. Our method is achieved by subjecting substrate motifs in 2-allyloxyenones to chiral organomagnesium reagents, which trigger the Claisen rearrangement upon direct 1,2-carbonyl addition. The observed diastereoselectivity of the allyl migration is proposed to originate from the intramolecular chelation of the magnesium alkoxide to the allyloxy moiety. American Chemical Society 2023-10-13 /pmc/articles/PMC10616857/ /pubmed/37830497 http://dx.doi.org/10.1021/acs.orglett.3c02752 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Badmus, Fatimat O.
Thombal, Raju S.
Philkhana, Satish Chandra
Malone, Joshua A.
Bailey, Christian E.
Armendariz-Gonzalez, Estefania
Mureka, Edward W.
Locicero, Cale M.
Fronczek, Frank R.
Kartika, Rendy
Directing the Stereoselectivity of the Claisen Rearrangement to Form Cyclic Ketones with Full Substitution at the α-Positions
title Directing the Stereoselectivity of the Claisen Rearrangement to Form Cyclic Ketones with Full Substitution at the α-Positions
title_full Directing the Stereoselectivity of the Claisen Rearrangement to Form Cyclic Ketones with Full Substitution at the α-Positions
title_fullStr Directing the Stereoselectivity of the Claisen Rearrangement to Form Cyclic Ketones with Full Substitution at the α-Positions
title_full_unstemmed Directing the Stereoselectivity of the Claisen Rearrangement to Form Cyclic Ketones with Full Substitution at the α-Positions
title_short Directing the Stereoselectivity of the Claisen Rearrangement to Form Cyclic Ketones with Full Substitution at the α-Positions
title_sort directing the stereoselectivity of the claisen rearrangement to form cyclic ketones with full substitution at the α-positions
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10616857/
https://www.ncbi.nlm.nih.gov/pubmed/37830497
http://dx.doi.org/10.1021/acs.orglett.3c02752
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