title: Lithiated imines: solvent-dependent aggregate structures and mechanisms of alkylation.
abstract: We describe efforts to understand the structure and reactivity of lithiated cyclohexanone N-cyclohexylimine. The lithioimine affords complex solvent-dependent distributions of monomers, dimers, and trimers in a number of ethereal solvents. Careful selection of solvent provides exclusively monosolvated dimers. Rate studies on the C-alkylations reveal chronic mixtures of monomer- and dimer-based pathways. We explore the factors influencing reactants and alkylation transition structures and the marked differences between lithioimines and isostructural lithium dialkylamides with the aid of density functional theory calculations.
authors.affiliation: Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, USA.
authors.forename: Stephan J
authors.initials: SJ
authors.lastname: Zuend
authors.forename: Antonio
authors.initials: A
authors.lastname: Ramirez
authors.forename: Emil
authors.initials: E
authors.lastname: Lobkovsky
authors.forename: David B
authors.initials: DB
authors.lastname: Collum
mesh_terms: D000478:Alkylation; D019281:Dimerization; D007097:Imines / Q000737:chemistry*; D007700:Kinetics; D008094:Lithium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure
chemical_list: D007097:Imines; D008094:Lithium