Platinum-catalyzed highly selective thiocarbonylation of acetylenes with thiols and carbon monoxide

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

“…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. A possible pathway may include the CO insertion into the S-Pt bond of PtH(SR)(PPh 3 ) 2 .…”

The Formation of Csp 2 S and Csp 2 Se Bonds by Substitution and Addition Reactions Catalyzed by Transition Metal Complexes

“…If Pt(PPh 3 ) 4 catalyst was utilized, the a,b-unsaturated thioester was formed as a major product (Scheme 3.90) [160]. The formation of trans-[PtH(SPh)(PPh 3 ) 2 ] in the catalytic cycle was proposed [161].…”

Thioesterifications Free of Activating Agent and Thiol: A Three‐Component Reaction of Carboxylic Acids, Thioureas, and Michael Acceptors

“…When the thioester 5ka wasf urther reactedw ith (S)-1-phenylethanamine,a mide 6 waso btained as as ingle product andn od iastereomeric isomerw as observed in 13 CNMR. This results uggestst hat the optical purityo f1k was preserved during this thioesterification [Eq.…”

“…[11] Recent progress in the preparation of thioesters includes the acid-catalyzed, direct condensation of carboxylic acids andt hiols, [12] and various coupling reactions,m ainly mediated by metal complexes. [13][14][15] An interesting development, recently reported by Caie tal.,d emonstrated that thioesters could be producedf rom ao ne-pot, three-component reactiono fo rganic halides,a romatica cyl halides,a nd thioureaa st he source of the sulfura tom (Scheme 1). [16] Herein, we report an ew thioesterification of carboxylic acids in which the adducts of thioureas and Michaela cceptors activate the carboxylic acids and also provide the corresponding thiolate to generate the thioesters.T his one-pot, three-componentr eaction is performed under mild conditions and is free of the use of reactive, often foul-smelling thiols andt he activating reagents frequently requiredf or the thioesterification of carboxylic acids.W eh ave found that the efficiencyo ft his process is further improved by addition of acatalytic amount of compound 4,aconjugate of athioureaa nd as econdary amine.…”

“…In addition to CH 2 Cl 2 ,o ther polar, aprotic solventss uch as toluene and DMFw ere compatible with this reaction( entries9 and 10), andt he reaction time could be shortened to 10 hb yincreasing the reaction temperature,b yu sing solventsw ith higher boiling points (entries 9a nd 11). However, the reaction failed in THF,m ethanol, or aqueous DMF solution (entries [12][13][14]. N,N'-Dimethylthiourea( 3b), commercially available as is 3a,w as also as uitable source of the sulfura tom (entries15a nd 16).…”