Nitrile anions: solvent-dependent cyclizations

Extensive cyclizations in hydrocarbon and polar solvents demonstrate a profound solvent sensitivity for intramolecular nitrile anion alkylations. S(N)i cyclizations enforce very precise steric constraints in the transition state, allowing correlation of the cyclization stereochemistry with the orbital orientation of the nitrile anion. Collectively the cyclizations suggest a continuum of nitrile anion transition states, varying from planar to fully pyramidal, that selectively cyclize to cis- and trans-decalins, respectively.