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1.2.3.6.2 Thiocarbonylation of Alkynes with Thiols and Carbon Monoxide

DOI: 10.1055/sos-SD-001-00206

Takacs, J. M.; Vayalakkada, S.; Jiang, X.Science of Synthesis, (20011306.

Palladium complexes bearing phosphine ligands, e.g. Pd(PPh3)4 and [PdCl2(PPh3)2], are effective catalysts for the thiocarbonylation of simple alkynes with thiols and carbon monoxide, but often the reaction results in a complex mixture of products.[‌43‌] However, the palladium-catalyzed thiocarbonylation of propargylic alcohols can be preparatively useful. Both palladium(0) and palladium(II) complexes possessing phosphine ligands display high catalytic activity. Depending upon the exact conditions, the reaction can be made to give a monothioester 173, a bis(thioester) 174, or a sulfur-bearing furanone 172 in good to excellent yield (Scheme 47). For example, the tetrakis(triphenylphosphine)palladium(0)-catalyzed reaction of a propargyl alcohol 171, a thiol (the ratio of propargyl alcohol to thiol is 1:1), and carbon monoxide (41atm) in tetrahydrofuran (110°C) with a catalytic amount of 4-toluenesulfonic acid affords the thioester 173 as the major product in 5285% yield.[‌44‌]

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