A copper-catalyzed 1,4-addition reaction of arylsulfonyl iodides with 1,3-enynes afforded various allenyl halides in high yields under mild conditions via a radical mechanism.

The CuBr2-catalyzed enantioselective allenylation of terminal alkynols with carbon chains of different lengths has been developed. Compared with (S)-α,α-diphenylprolinol, the reaction using (S)-α,α-dimethylprolinol as the chiral amine afforded optically active 1,3-disubstuted allenols with higher ee-values. Both aliphatic and aromatic aldehydes could be applied. The naturally occurring phlomic acid was synthesized in four steps from commercially available hex-5-yn-1-ol.