Photoredox Cleavage of a Csp3-Csp3 Bond in Aromatic Hydrocarbons.
J Am Chem Soc
; 145(22): 12284-12292, 2023 Jun 07.
Article
em En
| MEDLINE
| ID: mdl-37216226
ABSTRACT
Functionalizing molecules through the selective cleavage of carbon-carbon bonds is an attractive approach in synthetic chemistry. Despite recent advances in both transition-metal catalysis and radical chemistry, the selective cleavage of inert Csp3-Csp3 bonds in hydrocarbon feedstocks remains challenging. Examples reported in the literature typically involve substrates containing redox functional groups or highly strained molecules. In this article, we present a straightforward protocol for the cleavage and functionalization of Csp3-Csp3 bonds in alkylbenzenes using photoredox catalysis. Our method employs two distinct bond scission pathways. For substrates with tertiary benzylic substituents, a carbocation-coupled electron transfer mechanism is prevalent. For substrates with primary or secondary benzylic substituents, a triple single-electron oxidation cascade is applicable. Our strategy offers a practical means of cleaving inert Csp3-Csp3 bonds in molecules without any heteroatoms, resulting in primary, secondary, tertiary, and benzylic radical species.
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Base de dados:
MEDLINE
Idioma:
En
Ano de publicação:
2023
Tipo de documento:
Article