Generation and reactivity of α-metalated vinyl ethers

Oxygen‐Bearing Lithium Compounds in Modern Synthesis

“…The reaction is not usually stereospecific since a configurationally labile radical is involved. The chemistry of α-metalated derivatives of acyclic vinyl ethers, alkoxyallenes, and non-aromatic cyclic vinyl ethers has been reviewed [53]. Chapter 18 covers practical aspects of organolithium chemistry.…”

Density functional study of the lithiation of cyclic vinyl ethers in solution

“…These lithiated compounds have been mainly used as acyl anion synthons and as precursors of a-alkoxyalkenylcuprates in Kocienski's metallate rearrangement. 1 Lithiation of mid-sized cyclic vinyl ethers at vinylic versus allylic positions has been an active project in our group. Computational investigations of the lithiation of cyclic vinyl ethers in the gas phase at Hartree-Fock (geometry optimization) and second-order Møller-Plesset perturbation theory (single point) levels have suggested that in most cases, the vinylic positions are energetically favored.…”

Lithium Carbenoids

“…Thus, the lithiated ethers 56 and 54 function as an acetaldehyde d 1 synthon 177. The reactivity of α-metalated vinyl ethers has been reviewed recently 397 .…”