Selective C-C and C-H bond activation/cleavage of pinene derivatives: synthesis of enantiopure cyclohexenone scaffolds and mechanistic insights.
J Am Chem Soc
; 137(19): 6327-34, 2015 May 20.
Article
en En
| MEDLINE
| ID: mdl-25892479
ABSTRACT
The continued development of transition-metal-mediated C-C bond activation/cleavage methods would provide even more opportunities to implement novel synthetic strategies. We have explored the Rh(I)-catalyzed C-C activation of cyclobutanols resident in hydroxylated derivatives of pinene, which proceed in a complementary manner to the C-C bond cleavage that we have observed with many traditional electrophilic reagents. Mechanistic and computational studies have provided insight into the role of C-H bond activation in the stereochemical outcome of the Rh-catalyzed C-C bond activation process. Using this new approach, functionalized cyclohexenones that form the cores of natural products, including the spiroindicumides and phomactin A, have been accessed.
Texto completo:
1
Colección:
01-internacional
Base de datos:
MEDLINE
Asunto principal:
Rodio
/
Ciclobutanos
/
Ciclohexanonas
Idioma:
En
Revista:
J Am Chem Soc
Año:
2015
Tipo del documento:
Article
País de afiliación:
Estados Unidos