C(alkyl)-C(vinyl) bond cleavage enabled by Retro-Pallada-Diels-Alder reaction.
Nat Commun
; 14(1): 2572, 2023 May 04.
Article
em En
| MEDLINE
| ID: mdl-37142571
ABSTRACT
Activation and cleavage of carbon-carbon (C-C) bonds is a fundamental transformation in organic chemistry while inert C-C bonds cleavage remains a long-standing challenge. Retro-Diels-Alder (retro-DA) reaction is a well-known and important tool for C-C bonds cleavage but less been explored in methodology by contrast to other strategies. Herein, we report a selective C(alkyl)-C(vinyl) bond cleavage strategy realized through the transient directing group mediated retro-Diels-Alder reaction of a six-membered palladacycle, which is obtained from an in situ generated hydrazone and palladium hydride species. This unprecedented strategy exhibits good tolerances and thus offers new opportunities for late-stage modifications of complex molecules. DFT calculations revealed that an intriguing retro-Pd(IV)-Diels-Alder process is possibly involved in the catalytic cycle, thus bridging both Retro-Diels-Alder reaction and C-C bond cleavage. We anticipate that this strategy should prove instrumental for potential applications to achieve the modification of functional organic skeletons in synthetic chemistry and other fields involving in molecular editing.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Nat Commun
Assunto da revista:
BIOLOGIA
/
CIENCIA
Ano de publicação:
2023
Tipo de documento:
Article