Catalytic Ring Expansions of Cyclic Alcohols Enabled by Proton-Coupled Electron Transfer.
J Am Chem Soc
; 141(22): 8752-8757, 2019 06 05.
Article
em En
| MEDLINE
| ID: mdl-31117664
ABSTRACT
We report here a catalytic method for the modular ring expansion of cyclic aliphatic alcohols. In this work, proton-coupled electron transfer activation of an allylic alcohol substrate affords an alkoxy radical intermediate that undergoes subsequent C-C bond cleavage to furnish an enone and a tethered alkyl radical. Recombination of this alkyl radical with the revealed olefin acceptor in turn produces a ring-expanded ketone product. The regioselectivity of this C-C bond-forming event can be reliably controlled via substituents on the olefin substrate, providing a means to convert a simple N-membered ring substrate to either n+1 or n+2 ring adducts in a selective fashion.
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Base de dados:
MEDLINE
Assunto principal:
Prótons
/
Álcoois
Idioma:
En
Ano de publicação:
2019
Tipo de documento:
Article