Iridium-Catalyzed Intramolecular ß-C-H Alkenylation of Ketones with Alkynes via a Hydride-Transfer Approach.
J Am Chem Soc
; 144(50): 23230-23238, 2022 12 21.
Article
em En
| MEDLINE
| ID: mdl-36508583
ABSTRACT
Direct functionalization of carbonyl ß C-H bonds without using directing groups has not been a trivial task, and it is even more challenging to realize the corresponding atom-economical transformations with common alkenes or alkynes as the coupling partner. Here, we describe the development of an iridium-catalyzed intramolecular direct ß-alkenylation of ketones with regular alkynes. The reaction is redox neutral, avoids strong acids or bases, and tolerates various functional groups. The combined experimental and computational mechanistic studies reveal a hydride-transfer pathway, involving ketone α,ß-desaturation, iridium-hydride-mediated alkyne insertion, conjugate addition, and α-protonation.
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1
Base de dados:
MEDLINE
Assunto principal:
Alcinos
/
Irídio
Idioma:
En
Ano de publicação:
2022
Tipo de documento:
Article