Journal of Organic Chemistry 2013-04-19

Enantioselective synthesis of 5,7-bicyclic ring systems from axially chiral allenes using a Rh(I)-catalyzed cyclocarbonylation reaction.

Francois Grillet, Kay M Brummond

Index: J. Org. Chem. 78(8) , 3737-54, (2013)

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Abstract

A transfer of chirality in an intramolecular Rh(I)-catalyzed allenic Pauson-Khand reaction (APKR) to access tetrahydroazulenones, tetrahydrocyclopenta[c]azepinones and dihydrocyclopenta[c]oxepinones enantioselectively (22-99% ee) is described. The substitution pattern of the allene affected the transfer of chiral information. Complete transfer of chirality was obtained for all trisubstituted allenes, but loss of chiral information was observed for disubstituted allenes. This work constitutes the first demonstration of a transfer of chiral information from an allene to the 5-position of a cyclopentenone using a cyclocarbonylation reaction. The absolute configuration of the corresponding cyclocarbonylation product was also established, something that is rarely done.