Synthesis of α,β-Unsaturated α′-Haloketones through the Chemoselective Addition of Halomethyllithiums to Weinreb Amides

A straightforward synthesis of variously functionalized α,β-unsaturated α'-haloketones has been achieved through the chemoselective addition of halomethyllithium carbenoids to Weinreb amides at -78 °C. A comparative study employing the corresponding esters under the same reaction conditions pointed out that the instability of the tetrahedral intermediate formed from the latter is responsible for the observed formation of carbinols instead of the desired haloketones.