Modification of 1-Hexene Vinylidene Dimer into Primary and Tertiary Alkanethiols

Aliphatic thiols are in high demand in materials chemistry. Herein, a synthesis of thio-derivatives of 1-hexene vinylidene dimer is described. The approach, based on a hydroalumination reaction with further replacement of the organoaluminum function with sulfur using thiourea or dimethyl disulfide, provides anti-Markovnikov products, 2-butyloctane-1-thiol or 5-(methylsulfanylmethyl)undecane, in moderate yields. The reaction of a vinylidene dimer with phosphorus pentasulfide in the presence of catalytic amounts of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) selectively gives the Markovnikov product, 5-methylundecane-5-thiol, with a yield of up to 77%.