Lithiomethyl ethyl ether from chloromethyl ethyl ether via a DTBB-catalysed lithiation

Article abstract of DOI:10.1016/0040-4020(95)00993-0

The reaction of equimolar amounts of chloromethyl ethyl ether (1) and a carbonyl compound [Bu(n)CHO, Bu(t)CHO, PhCHO, Pr(i)₂CO, Bu(t)₂CO, (CH₂)₄CO, 2-cyclohexenone, PhCOMe] with an excess of lithium powder (1:7 molar ratio) and a catalytic amount of DTBB (5 mol%) in THF at 0°C (Method A) leads, after hydrolysis, to the corresponding hydroxyethers 2. The reaction can be also carried out in a two-step process: tandem lithiation at -90°C and reaction with the electrophile [Bu(n)CHO,(CH₂)₄CO, PhCOMe, PhMe₂SiCl, CO₂, PhCN, PhCONMe₂, CyNCO, PhN=CHPh] at -90 to -60°C (Method B).