Lithiated imines: solvent-dependent aggregate structures and mechanisms of alkylation.
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.
Zuend
Stephan J
SJ
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, USA.
Ramirez
Antonio
A
Lobkovsky
Emil
E
Collum
David B
DB
D000478:Alkylation; D019281:Dimerization; D007097:Imines / Q000737:chemistry*; D007700:Kinetics; D008094:Lithium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure
D007097:Imines; D008094:Lithium