ARENE-CATALYZED LITHIATION OF TRIFLATES AND TRIFLAMIDES UNDER BARBIER-TYPE CONDITIONS - AN INDIRECT TRANSFORMATION OF ALCOHOLS AND AMINES INTO ORGANOLITHIUM COMPOUNDS

The reaction of alkyl triflates 1 or allyl or benzyl triflamides 3 wit h an excess of lithium powder and a catalytic amount of naphthalene (4 mol %) in the presence of different electrophiles [Me(3)SiCl, (PrCHO) -C-i, Bu(t)CHO, PhCHO, 4-MeOC(6)H(4)CHO, CH3(CH2)(6)CHO, Et(2)CO, (CH2 )(5)CO, (c-C3H5)(2)CO, PhCOMe, 4-MeC(6)H(4)COPh, PhCH=NPh, n-C8H7CON(C H2)(4)] in THF at temperature ranging between -78 and 0 degrees C lead s, after hydrolysis with water, to the corresponding condensation prod ucts 2. When alpha,beta-unsaturated carbonyl compounds are used as ele ctrophilic compounds 1,2-(2-cyclohexenone) or 1,4-addition (cinnamalde hyde or benzylideneacetone) takes places depending on the electrophile used. Copyright (C) 1996 Elsevier Science Ltd