229467-63-4Relevant academic research and scientific papers
Platinum-catalyzed highly selective thiocarbonylation of acetylenes with thiols and carbon monoxide
Kawakami, Jun-Ichi,Mihara, Masanori,Kamiya, Ikuyo,Takeba, Mitsuhiro,Ogawa, Akiya,Sonoda, Noboru
, p. 3521 - 3526 (2003)
A novel carbonylative addition of thiols (RSH) to terminal acetylenes (R′-C≡CH) takes place successfully in the presence of platinum catalysts under the pressure of carbon monoxide, providing α,β-unsaturated thioesters (R′-C(C(O)SR)=CH2) in good yields regioselectively. This 'hydrothiocarbonylation' reaction of acetylenes may include the formation of the platinum sulfide complex as key species.
Rhodium-catalyzed hydrothiolation of alkynes with thiols for construction of sulfur-containing π-conjugated systems
Yoshimura, Aya,Nomoto, Akihiro,Ogawa, Akiya
, p. 2381 - 2389 (2014/06/24)
To synthesize sulfur-containing π-conjugated polymers, reaction conditions for rhodium-catalyzed hydrothiolation of terminal alkynes with arenethiols are optimized in detail. Under the optimized conditions, rhodium-catalyzed hydrothiolation of terminal al
Highly regio- and stereocontrolled synthesis of vinyl sulfides via transition-metal-catalyzed hydrothiolation of alkynes with thiols
Ogawa, Akiya,Ikeda, Takuma,Kimura, Kouichi,Hirao, Toshikazu
, p. 5108 - 5114 (2007/10/03)
Regio- and stereoselectivity in the hydrothiolation of alkynes with thiols in the presence of a variety of transition-metal catalysts is investigated in detail. Among the catalysts employed, RhCl(PPh3)3 exhibits excellent catalytic ability toward the anti-Markovnikov addition of thiols (ArSH) to alkynes (RC≡CH), which affords the corresponding vinylic sulfides (trans-RCH=CHSAr) regio- and stereoselectively. The reaction may proceed by the formation of hydrorhodium sulfide species (H-[Rh]-SAr) and probably via the subsequent hydrorhodation of alkynes to provide vinylrhodium intermediates (RCH=CH-[Rh]-SAr). In contrast, PdCl2(PhCN)2-catalyzed hydrothiolation of aromatic alkynes (ArC≡CH) takes place to give the corresponding Markovnikov adducts (R(ArS)C=CH2) with excellent regioselectivity, probably via thiopalladation of alkynes by palladium sulfide species (ArS-[Pd]-Cl), which may be formed by ligand-exchange reaction between PdCl2(PhCN)2 and ArSH. Furthermore, in the case of alkynes bearing propargylic protons (R'CH2C≡CH), a sequential addition/isomerization reaction occurs to provide the internal vinylic sulfides (R'CH=C(SAr)CH3) regioselectively. From the same starting materials (alkyne and thiol), therefore, the regioselectivity of hydrothiolation can be attained simply by changing the catalysts, i.e., RhCl(PPh3)3 and PdCl2(PhCN)2.
