Cation-π Interactions in the Benzylic Arylation of Toluenes with Bimetallic Catalysts.
J Am Chem Soc
; 140(39): 12415-12423, 2018 10 03.
Article
en En
| MEDLINE
| ID: mdl-30185030
ABSTRACT
A method to directly arylate toluene derivatives with aryl bromides to generate diarylmethanes, which are important building blocks in drug discovery, is described. In this method, KN(SiMe3)2 in combination with a (NIXANTPHOS)Pd catalyst accomplished the deprotonative activation of toluene derivatives to permit cross-coupling with aryl bromides. Good to excellent yields are obtained with a range of electron-rich to neutral aryl bromides. Both electron-rich and electron-poor toluene derivatives are well tolerated, and even 2-chlorotoluene performs well, providing a platform for introduction of additional functionalization. This discovery hinges on the use of a main group metal to activate toluene for deprotonation by means of a cation-π interaction, which is secured by a bimetallic K(NIXANTPHOS)Pd assembly. Mechanistic and computational studies support acidification of toluene derivatives by the K+-cation- π interaction, which may prove pertinent in the development of other, new reaction systems.
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1
Banco de datos:
MEDLINE
Asunto principal:
Tolueno
/
Compuestos de Bifenilo
Idioma:
En
Año:
2018
Tipo del documento:
Article