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Chemistry ; 16(17): 5173-83, 2010 May 03.
Artigo em Inglês | MEDLINE | ID: mdl-20340116

RESUMO

Novel [{RhCl(CO)dppp}(2)]-catalyzed intramolecular carbonylative [2+2+1] cycloadditions of bis(phenylsulfonylallene) derivatives under CO, leading to the facile formation of bis(phenylsulfonyl)bicyclo[n.3.0] frameworks (n=4-6), have been developed. The terminal double bonds of both allenyl moieties served exclusively as the two pi-components. In particular, this newly developed method was shown to be a powerful tool for the construction of bicyclo[6.3.0]undecadienones, which have hardly been prepared by the known Pauson-Khand (-type) reactions. The bicyclo[7.3.0]dodecadienone homologue (one extra carbon) could be formed in rather low yields. Alternatively, novel cycloisomerizations of bis(phenylsulfonylallene) derivatives with catalysis by the same Rh(I) complex under N(2) readily produced the 3,4-dimethylene-2,5-bis(phenylsulfonyl)cyclononene and the corresponding cyclooctene and cycloheptene frameworks.


Assuntos
Alcadienos/síntese química , Técnicas de Química Combinatória , Ródio/química , Sulfonas/síntese química , Alcadienos/química , Catálise , Ciclização , Estrutura Molecular , Estereoisomerismo , Sulfonas/química
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