The reaction of 1,3-dicloro-2-butene (1; 5:1 Z:E-mixture) with lithium powder and a catalytic amount of 4,4 0 -di-tertbutylbiphenyl (DTBB, 1% molar) in the presence of different electrophiles [EtCHO, Pr i CHO, Bu t CHO, c-C 6 H 11 CHO, Me 2 CO, Et 2 CO, (CH 2 ) 4 CO, (CH 2 ) 5 CO, (c-C 3 H 5 ) 2 CO, Me 3 SiCl] in THF at temperatures ranging between 278 and 2508C gives, after hydrolysis with water, the corresponding products 2 in different Z:E-ratios depending on the electrophile used. Treatment of some diols 2 with hydrochloric acid gives dienic alcohols 3 or substituted dihydropyrans 4, depending on the structure of the starting diol. Finally, the same dichlorinated starting material is transformed into the corresponding allylic amines derived from morpholine and benzyl methyl amine and submitted to the same DTBB-catalysed lithiation as above, so after reaction with different electrophiles [Bu t CHO, c-C 6 H 11 CHO, Me 2 CO, Et 2 CO, (CH 2 ) 4 CO, (CH 2 ) 5 CO, Me 3 SiCl] and final hydrolysis with water, compounds 7 are isolated having a Z-configuration. A mechanistic explanation for this behaviour is given.