Metalated nitriles: cation-controlled cyclizations.

ABSTRACT: Judicious choice of cation allows the selective cyclization of substituted gamma-hydroxynitriles to trans- or cis-decalins and trans- or cis-bicyclo[5.4.0]undecanes. The stereoselectivities are consistent with deprotonations generating two distinctly different metalated nitriles: an internally coordinated nitrile anion with BuLi, and a C-magnesiated nitrile with i-PrMgCl. Employing cations to control the geometry of metalated nitriles permits stereodivergent cyclizations with complete control over the stereochemistry of the quaternary, nitrile-bearing carbon.

SUBMITTER: Fleming FF 

PROVIDER: S-EPMC2533635 | biostudies-literature | 2007 Jul

REPOSITORIES: biostudies-literature