Enantioselective Addition of Remote Alkyl Radicals to Double Bonds by Photocatalytic Proton-Coupled Electron Transfer (PCET) Deconstruction of Unstrained Cycloalkanols

[Image: see text] Herein, we report the enantioselective addition of remote alkyl radicals, generated from the ring opening of unstrained cycloalkanols by a proton-coupled electron transfer (PCET) process, to 2-acyl imidazoles previously coordinated to a rhodium-based chiral Lewis acid. High yields...

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Autores principales: Salaverri, Noelia, Carli, Benedetta, Díaz-Tendero, Sergio, Marzo, Leyre, Alemán, José
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9087350/
https://www.ncbi.nlm.nih.gov/pubmed/35362991
http://dx.doi.org/10.1021/acs.orglett.2c00662
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author Salaverri, Noelia
Carli, Benedetta
Díaz-Tendero, Sergio
Marzo, Leyre
Alemán, José
author_facet Salaverri, Noelia
Carli, Benedetta
Díaz-Tendero, Sergio
Marzo, Leyre
Alemán, José
author_sort Salaverri, Noelia
collection PubMed
description [Image: see text] Herein, we report the enantioselective addition of remote alkyl radicals, generated from the ring opening of unstrained cycloalkanols by a proton-coupled electron transfer (PCET) process, to 2-acyl imidazoles previously coordinated to a rhodium-based chiral Lewis acid. High yields and enantioselectivites up to 99% are achieved in 1 h. Mechanistic investigations support the formation of the remote alkyl radical by a PCET process, and theoretical studies explain the observed stereochemistry in the addition step.
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spelling pubmed-90873502022-05-11 Enantioselective Addition of Remote Alkyl Radicals to Double Bonds by Photocatalytic Proton-Coupled Electron Transfer (PCET) Deconstruction of Unstrained Cycloalkanols Salaverri, Noelia Carli, Benedetta Díaz-Tendero, Sergio Marzo, Leyre Alemán, José Org Lett [Image: see text] Herein, we report the enantioselective addition of remote alkyl radicals, generated from the ring opening of unstrained cycloalkanols by a proton-coupled electron transfer (PCET) process, to 2-acyl imidazoles previously coordinated to a rhodium-based chiral Lewis acid. High yields and enantioselectivites up to 99% are achieved in 1 h. Mechanistic investigations support the formation of the remote alkyl radical by a PCET process, and theoretical studies explain the observed stereochemistry in the addition step. American Chemical Society 2022-04-01 2022-05-06 /pmc/articles/PMC9087350/ /pubmed/35362991 http://dx.doi.org/10.1021/acs.orglett.2c00662 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 Salaverri, Noelia
Carli, Benedetta
Díaz-Tendero, Sergio
Marzo, Leyre
Alemán, José
Enantioselective Addition of Remote Alkyl Radicals to Double Bonds by Photocatalytic Proton-Coupled Electron Transfer (PCET) Deconstruction of Unstrained Cycloalkanols
title Enantioselective Addition of Remote Alkyl Radicals to Double Bonds by Photocatalytic Proton-Coupled Electron Transfer (PCET) Deconstruction of Unstrained Cycloalkanols
title_full Enantioselective Addition of Remote Alkyl Radicals to Double Bonds by Photocatalytic Proton-Coupled Electron Transfer (PCET) Deconstruction of Unstrained Cycloalkanols
title_fullStr Enantioselective Addition of Remote Alkyl Radicals to Double Bonds by Photocatalytic Proton-Coupled Electron Transfer (PCET) Deconstruction of Unstrained Cycloalkanols
title_full_unstemmed Enantioselective Addition of Remote Alkyl Radicals to Double Bonds by Photocatalytic Proton-Coupled Electron Transfer (PCET) Deconstruction of Unstrained Cycloalkanols
title_short Enantioselective Addition of Remote Alkyl Radicals to Double Bonds by Photocatalytic Proton-Coupled Electron Transfer (PCET) Deconstruction of Unstrained Cycloalkanols
title_sort enantioselective addition of remote alkyl radicals to double bonds by photocatalytic proton-coupled electron transfer (pcet) deconstruction of unstrained cycloalkanols
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9087350/
https://www.ncbi.nlm.nih.gov/pubmed/35362991
http://dx.doi.org/10.1021/acs.orglett.2c00662
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