The First Example of Transition-Metal-Catalyzed Thioformylation of Acetylenes with Aromatic Thiols and Carbon Monoxide

Organometallic Approaches to Carbon–Sulfur Bond Formation

“…Observed regioselectivity in the Pd (OAc) 2 catalyzed alkyne hydrothiolation [151] Since this initial report, significant advances have been made with Ni [121,[152][153][154][155][156][157][158][159], Pd , Pt [187,[190][191][192][193][194][195][196][197][198][199][200][201], Rh [202][203][204][205][206][207][208][209][210][211][212] and Ir [204,211]. In general, group 10 metals generate the branched isomer and proceed by syninsertion of the alkyne into an M-S bond, followed by protonolysis of the resulting M-C bond, although this is dependent on the reaction conditions.…”

Unusual Influence of the Structures of Transition Metal Complexes on Catalytic C–S and C–Se Bond Formation Under Homogeneous and Heterogeneous Conditions

“…[69,70] Use of palladium complexes resulted in the formation of complex mixtures of compounds including both mono-(25 % of 22 + 23) and bisthiolation (7 % of 6) products. [69] Use of platinum as a catalyst resulted in selective formation of α,β-unsaturated thioester 22 in good yields (70-94 %) and regioselectivities. [70] Rhodium catalyst gave reversed regioselectivity, providing product 24 in good yields of 52-82 % and in a broad range of E/Z ratios depending on the substituents (E/Z = 1:99-86:14).…”

Transition-Metal-Catalyzed S–H and Se–H Bonds Addition to Unsaturated Molecules

“…These reactions provide useful tools to synthetically important organosulfur compounds [104,105]. For example, the rhodium-catalyzed reaction of alkynes with thiols and CO provides the corresponding thioformylation products regioselectively [106,107]. Switching the catalyst from rhodium complex to platinum complex leads to a sharp reversal of regioselectivity of CO introduction [108,109] The latter carbonylation involves the formation of PtH(SR)(PPh 3 ) 2 by the oxidative addition of RSH to the zero-valent platinum complex.…”