Decarbonylation of Salicylaldehyde Activated by p‐Cymene Ruthenium(II) Dimer: Implication for Catalytic Alkyne Hydrothiolation

A stoichiometric C–H activation/decarbonylation of salicylaldehyde by [(η6-p-cymene)RuCl2]2 gave a carbonyl derivative [(η6-p-cymene)RuCl(CO)(Ph-O)] (1) without the use of CO gas. A variety of polar phosphines were then incorporated into compound 1 to give new RuII cationic catalysts, [(η6-p-cymene)Ru(CO)(Ph-O)L]BF4 (2–8). These were used to catalyse the hydrothiolation of alkynes with a range of thiols in aqueous THF to give anti-Markovnikov E-linear vinyl sulfides in high yields.