94074-96-1

Upstream product

• 765-03-7 1-dodecyne 
• 108-98-5 thiophenol 
• 104849-58-3 (E)-1-(triphenylstannyl)-1-dodecene 

Relevant academic research and scientific papers

Highly stereoselective anti-Markovnikov hydrothiolation of alkynes and electron-deficient alkenes by a supported Cu-NHC complex

A practical, efficient, and low-cost heterogeneous catalyst consisting of a Cu-NHC (N-heterocyclic carbene) complex grafted to SBA-15 silica for the catalytic hydrothiolation of alkynes and electron-deficient alkenes under mild reaction conditions has been developed. The heterogeneous catalyst displays higher activity and stereoselectivity to Z-anti-Markovnikov isomers compared with the homogeneous analog under otherwise identical reaction conditions. The catalytic system is applicable to a broad range of alkynes and thiols and is recyclable without significant loss in catalytic performance. High activity and perfect selectivity to alkyl sulfides formed by the addition of electron-deficient alkenes to various thiols catalyzed by the supported Cu-NHC complex were also realized. This journal is the Partner Organisations 2014.

Highly regio- and stereoselective hydrothiolation of acetylenes with thiols catalyzed by a well-defined supported Rh complex

Highly regio- and stereoselective hydrothiolation of a wide range of alkynes with various thiols was demonstrated in the presence of a well-defined Rh complex supported on mesoporous SBA-15 silica. The catalyst was easily recovered and reused several times without significant loss of activity or selectivity.

Highly regio- and stereocontrolled synthesis of vinyl sulfides via transition-metal-catalyzed hydrothiolation of alkynes with thiols

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.

Application of Free Radical Substitution Reaction into Interconversion of 1-Alkenylsulfides, 1-Alkenylgermanes, and 1-Alkenylstannanes

Treatment of 1-alkenylsulfides or 1-alkenylstannanes with Ph3GeH in the presence of Et3B provides 1-alkenyltriphenylgermanes in good yields. 1-Alkenylstannanes are converted into 1-alkenylsulfides easily with PhSH-Et3B, whereas 1-alkenyltriphenylgermanes are recovered unchanged upon treatment with Ph3SnH-Et3B or PhSH-Et3B.