Metalated Nitriles: Stereodivergent Cation-Controlled Cyclizations1.

ABSTRACT: Stereodivergent cyclizations of gamma-hydroxy cyclohexanecarbonitriles are controlled simply through judicious choice of cation in the alkylmetal base. Deprotonating a series of cyclic gamma-hydroxy nitriles with i-PrMgBr generates C-magnesiated nitriles that cyclize under stereoelectronic control to cis-fused hydrindanes, decalins, and bicyclo [5.4.0] undecanes. An analogous deprotonation with BuLi triggers cyclization to trans-fused hydrindanes, decalins, and bicyclo [5.4.0] undecanes consistent with a sterically controlled electrophilic attack on an equatorial nitrile anion. Using cations to control the geometry of metalated nitriles provides a versatile, stereodivergent cyclization to cis- and trans-hydrindanes, decalins, and [5. 4. 0] undecanes, and reveals the key geometric requireme

SUBMITTER: Fleming FF 

PROVIDER: S-EPMC2597827 | biostudies-literature | 2008 Aug

REPOSITORIES: biostudies-literature