144482-35-9

Upstream product

• 17414-08-3 2-<(phenylthio)methyl>tetrahydrofuran 
• 882-33-7 diphenyldisulfane 
• 5390-04-5 pent-1-yn-5-ol 
• 108-98-5 thiophenol 
• 111341-49-2 phenylthio-4-pentenol 
• 821-09-0 n-Pent-4-enyl alcohol 
• 280574-88-1 O-(2'-tetrahydropyranyl)-5-phenylthiopent-4-ynol 
• 420112-82-9 (E)-O-(2'-tetrahydropyranyl)-5-phenylthiopent-4-enol 
• 111341-51-6 4-chloro-5-phenylthiopentanol 

Downstream Products

• 111341-52-7 (E/Z)-5-phenylthio-4-penten-1-ol 
• 20965-36-0 2-(phenylthio)tetrahydro-2H-pyran 

Relevant academic research and scientific papers

Evolution of a Polyene Cyclization Cascade for the Total Synthesis of (?)-Cyclosmenospongine

We report a full account on the development of a unique cationic polyene cyclization for the total synthesis of the tetracyclic meroterpenoid (?)-cyclosmenospongine. A highly convergent three-component coupling strategy enabled rapid access to individual cyclization precursors that were tested for their reactivity. The successful transformation generates three rings and sets four consecutive stereocenters in a single operation proceeding in a highly efficient manner to give exclusively the trans-decalin framework. In addition, we found that the enol ether geometry and the relative configuration of C3 and C8 are crucial for the success of the polyene cyclization.

Air Oxidative Radical Oxysulfurization of Alkynes Leading to α-Thioaldehydes

Air oxidative radical oxysulfurization of alkynes initiated by 0.5 mol % tert-butyl hydroperoxide with arylthiols is described. The reaction proceeded at room temperature in the presence of 5% mol water to afford selective α-thioaldehydes. (Chemical Equation Presented).

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.

Heterogeneous hydrothiolation of alkynes with thiols catalyzed by diphosphino-functionalized MCM-41 anchored rhodium complex

A novel diphosphino-functionalized MCM-41 anchored rhodium complex [MCM-41-2P-RhCl(PPh3)] was conveniently synthesized by the reaction of diphosphino-functionalized MCM-41 (MCM-41-2P) with RhCl(PPh3) 3. It was found that this rhodium complex is an efficient catalyst for the hydrothiolation of terminal alkynes with thiols and can be recovered and recycled by a simple filtration of the reaction solution and used for at least ten consecutive trials without any decreases in activity.

Intramolecular carbolithiation reactions of chiral alpha-amino-organolithium species.

Enantiomerically enriched alpha-amino-organolithium species, in which the lithium atom is attached to a stereogenic carbon centre, have been found to be chemically stable at room temperature in a solvent of very low polarity and undergo intramolecular car

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.

CYCLIC ETHER SYNTHESIS: SULFENYLETHERIFICATION WITH BENZENESULFENYL CHLORIDE/N,N-DIISOPROPYLETHYLAMINE AND SULFENATE ESTER CYCLOADDITIONS

A general method for the formation of the cyclic ethers 9, 10, 13, 14, 16 and the lactone 30 is described.The procedure employs benzenesulfenyl chloride prepared in situ in acetonitrile and N,N-diisopropylethylamine to generate a thiiranium (episulfonium) ion intermediate from which the cyclic products arise by internal nucleophilic displacement.In the special case of the norbornene alcohols 1 and 2 the oxethanes 5 and 6 are formed by intramolecular sulfenate ester cycloaddition.