Enantioselective Intramolecular Iridium-Catalyzed Cyclopropanation of α-Carbonyl Sulfoxonium Ylides

[Image: see text] Enantioselective cyclopropanation of α-carbonyl sulfoxonium ylides (SY) has so far been limited to addition/ring closure reactions on electron-poor olefins. Herein, we report the iridium-catalyzed intramolecular cyclopropanation of SY in the presence of a chiral diene in up to 96%...

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Autores principales: Vidal, Lucas, Chen, Pan-Pan, Nicolas, Eva, Hackett, Andrew, Robertson, Craig M., Houk, Kendall N., Aïssa, Christophe
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9706811/
https://www.ncbi.nlm.nih.gov/pubmed/36367970
http://dx.doi.org/10.1021/acs.orglett.2c03396
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author Vidal, Lucas
Chen, Pan-Pan
Nicolas, Eva
Hackett, Andrew
Robertson, Craig M.
Houk, Kendall N.
Aïssa, Christophe
author_facet Vidal, Lucas
Chen, Pan-Pan
Nicolas, Eva
Hackett, Andrew
Robertson, Craig M.
Houk, Kendall N.
Aïssa, Christophe
author_sort Vidal, Lucas
collection PubMed
description [Image: see text] Enantioselective cyclopropanation of α-carbonyl sulfoxonium ylides (SY) has so far been limited to addition/ring closure reactions on electron-poor olefins. Herein, we report the iridium-catalyzed intramolecular cyclopropanation of SY in the presence of a chiral diene in up to 96% yield and 98% enantioselectivity. Moreover, density functional theory calculations suggest that the re face of the olefin preferably attacks an iridium carbene intermediate in an asynchronous concerted step that is independent of the geometry of the olefin.
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spelling pubmed-97068112022-11-30 Enantioselective Intramolecular Iridium-Catalyzed Cyclopropanation of α-Carbonyl Sulfoxonium Ylides Vidal, Lucas Chen, Pan-Pan Nicolas, Eva Hackett, Andrew Robertson, Craig M. Houk, Kendall N. Aïssa, Christophe Org Lett [Image: see text] Enantioselective cyclopropanation of α-carbonyl sulfoxonium ylides (SY) has so far been limited to addition/ring closure reactions on electron-poor olefins. Herein, we report the iridium-catalyzed intramolecular cyclopropanation of SY in the presence of a chiral diene in up to 96% yield and 98% enantioselectivity. Moreover, density functional theory calculations suggest that the re face of the olefin preferably attacks an iridium carbene intermediate in an asynchronous concerted step that is independent of the geometry of the olefin. American Chemical Society 2022-11-11 2022-11-25 /pmc/articles/PMC9706811/ /pubmed/36367970 http://dx.doi.org/10.1021/acs.orglett.2c03396 Text en © 2022 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 Vidal, Lucas
Chen, Pan-Pan
Nicolas, Eva
Hackett, Andrew
Robertson, Craig M.
Houk, Kendall N.
Aïssa, Christophe
Enantioselective Intramolecular Iridium-Catalyzed Cyclopropanation of α-Carbonyl Sulfoxonium Ylides
title Enantioselective Intramolecular Iridium-Catalyzed Cyclopropanation of α-Carbonyl Sulfoxonium Ylides
title_full Enantioselective Intramolecular Iridium-Catalyzed Cyclopropanation of α-Carbonyl Sulfoxonium Ylides
title_fullStr Enantioselective Intramolecular Iridium-Catalyzed Cyclopropanation of α-Carbonyl Sulfoxonium Ylides
title_full_unstemmed Enantioselective Intramolecular Iridium-Catalyzed Cyclopropanation of α-Carbonyl Sulfoxonium Ylides
title_short Enantioselective Intramolecular Iridium-Catalyzed Cyclopropanation of α-Carbonyl Sulfoxonium Ylides
title_sort enantioselective intramolecular iridium-catalyzed cyclopropanation of α-carbonyl sulfoxonium ylides
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9706811/
https://www.ncbi.nlm.nih.gov/pubmed/36367970
http://dx.doi.org/10.1021/acs.orglett.2c03396
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