Migrative Carbofluorination of Saturated Amides Enabled by Pd-Based Dyotropic Rearrangement.
J Am Chem Soc
; 144(31): 14047-14052, 2022 08 10.
Article
em En
| MEDLINE
| ID: mdl-35916403
ABSTRACT
Directly editing an all-carbon quaternary carbon itself of nonstrained acyclic molecules remains underexploited despite the recent advances in the fields of both C-H and C-C bond activation. Herein, we report a palladium-catalyzed migrative carbofluorination of saturated amides enabled by the activation of both the C(sp3)-H and the Cquaternary-Cσ bonds. In this transformation, the α-quaternary carbon of Weinreb amides is converted to α-tertiary fluoride with concurrent migration of an aryl or an amido group from the α- to ß-carbon. DFT calculations indicate that the dyotropic rearrangement proceeds through an unusual anti-selective [2.1.0] bicyclic transition state. The reaction, compatible with a broad range of functional groups, is stereospecific and is applicable to the synthesis of enantioenriched products.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Paládio
/
Amidas
Idioma:
En
Revista:
J Am Chem Soc
Ano de publicação:
2022
Tipo de documento:
Article
País de afiliação:
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