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Cobalt bis(acetylacetonate)–tert-butyl hydroperoxide–triethylsilane: a general reagent combination for the Markovnikov-selective hydrofunctionalization of alkenes by hydrogen atom transfer

We show that cobalt bis(acetylacetonate) [Co(acac)(2)], tert-butyl hydroperoxide (TBHP), and triethylsilane (Et(3)SiH) constitute an inexpensive, general, and practical reagent combination to initiate a broad range of Markovnikov-selective alkene hydrofunctionalization reactions. These transformatio...

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Autores principales: Ma, Xiaoshen, Herzon, Seth B
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6122341/
https://www.ncbi.nlm.nih.gov/pubmed/30202480
http://dx.doi.org/10.3762/bjoc.14.201
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author Ma, Xiaoshen
Herzon, Seth B
author_facet Ma, Xiaoshen
Herzon, Seth B
author_sort Ma, Xiaoshen
collection PubMed
description We show that cobalt bis(acetylacetonate) [Co(acac)(2)], tert-butyl hydroperoxide (TBHP), and triethylsilane (Et(3)SiH) constitute an inexpensive, general, and practical reagent combination to initiate a broad range of Markovnikov-selective alkene hydrofunctionalization reactions. These transformations are believed to proceed by cobalt-mediated hydrogen atom transfer (HAT) to the alkene substrate, followed by interception of the resulting alkyl radical intermediate with a SOMOphile. In addition, we report the first reductive couplings of unactivated alkenes and aryldiazonium salts by an HAT pathway. The simplicity and generality of the Co(acac)(2)–TBHP–Et(3)SiH reagent combination suggests it as a useful starting point to develop HAT reactions in complex settings.
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spelling pubmed-61223412018-09-10 Cobalt bis(acetylacetonate)–tert-butyl hydroperoxide–triethylsilane: a general reagent combination for the Markovnikov-selective hydrofunctionalization of alkenes by hydrogen atom transfer Ma, Xiaoshen Herzon, Seth B Beilstein J Org Chem Full Research Paper We show that cobalt bis(acetylacetonate) [Co(acac)(2)], tert-butyl hydroperoxide (TBHP), and triethylsilane (Et(3)SiH) constitute an inexpensive, general, and practical reagent combination to initiate a broad range of Markovnikov-selective alkene hydrofunctionalization reactions. These transformations are believed to proceed by cobalt-mediated hydrogen atom transfer (HAT) to the alkene substrate, followed by interception of the resulting alkyl radical intermediate with a SOMOphile. In addition, we report the first reductive couplings of unactivated alkenes and aryldiazonium salts by an HAT pathway. The simplicity and generality of the Co(acac)(2)–TBHP–Et(3)SiH reagent combination suggests it as a useful starting point to develop HAT reactions in complex settings. Beilstein-Institut 2018-08-28 /pmc/articles/PMC6122341/ /pubmed/30202480 http://dx.doi.org/10.3762/bjoc.14.201 Text en Copyright © 2018, Ma and Herzon https://creativecommons.org/licenses/by/4.0https://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0). Please note that the reuse, redistribution and reproduction in particular requires that the authors and source are credited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms)
spellingShingle Full Research Paper
Ma, Xiaoshen
Herzon, Seth B
Cobalt bis(acetylacetonate)–tert-butyl hydroperoxide–triethylsilane: a general reagent combination for the Markovnikov-selective hydrofunctionalization of alkenes by hydrogen atom transfer
title Cobalt bis(acetylacetonate)–tert-butyl hydroperoxide–triethylsilane: a general reagent combination for the Markovnikov-selective hydrofunctionalization of alkenes by hydrogen atom transfer
title_full Cobalt bis(acetylacetonate)–tert-butyl hydroperoxide–triethylsilane: a general reagent combination for the Markovnikov-selective hydrofunctionalization of alkenes by hydrogen atom transfer
title_fullStr Cobalt bis(acetylacetonate)–tert-butyl hydroperoxide–triethylsilane: a general reagent combination for the Markovnikov-selective hydrofunctionalization of alkenes by hydrogen atom transfer
title_full_unstemmed Cobalt bis(acetylacetonate)–tert-butyl hydroperoxide–triethylsilane: a general reagent combination for the Markovnikov-selective hydrofunctionalization of alkenes by hydrogen atom transfer
title_short Cobalt bis(acetylacetonate)–tert-butyl hydroperoxide–triethylsilane: a general reagent combination for the Markovnikov-selective hydrofunctionalization of alkenes by hydrogen atom transfer
title_sort cobalt bis(acetylacetonate)–tert-butyl hydroperoxide–triethylsilane: a general reagent combination for the markovnikov-selective hydrofunctionalization of alkenes by hydrogen atom transfer
topic Full Research Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6122341/
https://www.ncbi.nlm.nih.gov/pubmed/30202480
http://dx.doi.org/10.3762/bjoc.14.201
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AT herzonsethb cobaltbisacetylacetonatetertbutylhydroperoxidetriethylsilaneageneralreagentcombinationforthemarkovnikovselectivehydrofunctionalizationofalkenesbyhydrogenatomtransfer