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.
Fleming
Fraser F
FF
Department of Chemistry & Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282-1530, USA. flemingf@duq.edu
Shook
Brian C
BC
D000838:Anions / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000737:chemistry; D002384:Catalysis; D002625:Chemistry, Organic / Q000379:methods; D018360:Crystallography, X-Ray; D003500:Cyclization; D003510:Cyclohexanes / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009281:Naphthalenes / Q000737:chemistry; D009570:Nitriles / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
C463240:2-(4-chlorobutyl)cyclohexanecarbonitrile; C463279:5-(methylthiothioxoomethoxy)bicyclo(4.4.0)decanecarbonitrile; D000838:Anions; D001643:Bridged Bicyclo Compounds; D003510:Cyclohexanes; D009281:Naphthalenes; D009570:Nitriles; C463280:bicyclo(4.4.0)decanecarbonitrile; C007229:decalin