ja992062z_si_001.pdf (322.01 kB)
Lithium Diisopropylamide-Mediated Enolizations: Solvent-Independent Rates, Solvent-Dependent Mechanisms
journal contribution
posted on 2000-03-02, 00:00 authored by Xiufeng Sun, David B. CollumRate studies of a lithium diisopropylamide-mediated ester enolization reveal solvation effects that
are not in accord with expectation. Metalations in THF, t-BuOMe, HMPA/THF, and DMPU/THF (HMPA =
hexamethylphosphoramide, DMPU = 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidone) occur at nearly the
same rates, yet proceed via four fundamentally distinct scenarios: (1) disolvated monomer in THF, (2)
monosolvated dimer in t-BuOMe, (3) both monosolvated monomer and tetrasolvated dimer in HMPA/THF,
and (4) mono- and disolvated monomers in DMPU/THF. The implication of reactive open dimers in t-BuOMe
and triple ions in HMPA/THF underscores the importance of aggregate-based reactions.