Arene-catalysed lithiation of triflates and triflamides under Barbier-type conditions: An indirect transformation of alcohols and amines into organolithium compounds

Article abstract of DOI:10.1016/0040-4020(96)00886-1

The reaction of alkyl triflates 1 or benzyl triflamides 3 with an excess of lithium powder and a catalytic amount of naphthalene (4 mol%) in the presence of different electrophiles [Me₃SiCl, Pr(i)CHO, Bu(t)CHO, PhCHO, 4-MeOC₆H₄-CHO, CH₃(CH₂)₆CHO, Et₂CO, (CH₂)₅CO, (c-C₃H₅)₂CO, PhCOMe, 4-MeC₆H₄COPh, PhCh=NPh, n-C₈H₇CON(CH₂)₄] in THF at temperature ranging between -78 and 0°C leads, after hydrolysis with water, to the corresponding condensation products 2. When α,β-unsaturated carbonyl compounds are used as electrophilic compounds 1,2- (3-cyclohexenone) or 1,4-addition (cinnamaldehyde or benzylideneacetone) takes place depending on the electrophile used.