Rhodium-catalyzed carbon-silicon bond activation for synthesis of benzosilole derivatives.
J Am Chem Soc
; 134(47): 19477-88, 2012 Nov 28.
Article
em En
| MEDLINE
| ID: mdl-23126446
ABSTRACT
A rhodium-catalyzed coupling reaction of 2-trimethylsilylphenylboronic acid with internal alkynes is developed for the synthesis of 2,3-disubstituted benzosilole derivatives. A range of functional groups, encompassing ketones, esters, amines, aryl bromides, and heteroarenes, are compatible, which provides rapid access to diverse benzosiloles. Sequential 2-fold coupling enables modular synthesis of asymmetrically substituted 1,5-dihydro-1,5-disila-s-indacene, a π-extended molecule of interest in organic electronics. In terms of the mechanism, the reaction involves cleavage of a C(alkyl)-Si bond in a trialkylsilyl group, which normally requires extremely harsh conditions for activation. Mechanistic studies, including effects of substituents, reveal that C-Si bond cleavage does not proceed through a hypercoordinated silicon species, but rather through a rhodium-mediated activation process. The potential use of the reaction in catalytic asymmetric synthesis of Si-chiral benzosiloles is also demonstrated.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Compostos Organometálicos
/
Ródio
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Silício
/
Carbono
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Compostos de Organossilício
Idioma:
En
Revista:
J Am Chem Soc
Ano de publicação:
2012
Tipo de documento:
Article
País de afiliação:
Japão