34043-60-2Relevant academic research and scientific papers
Catalytic Hydrothiolation: Regio- and Enantioselective Coupling of Thiols and Dienes
Yang, Xiao-Hui,Davison, Ryan T.,Dong, Vy M.
, p. 10443 - 10446 (2018)
We report a Rh-catalyzed hydrothiolation of 1,3-dienes, including petroleum feedstocks. Either secondary or tertiary allylic sulfides can be generated from the selective addition of a thiol to the more substituted double bond of a diene. The catalyst tolerates a wide range of functional groups, and the loading can be as low as 0.1 mol %.
Pd/BIPHEPHOS is an Efficient Catalyst for the Pd-Catalyzed S-Allylation of Thiols with High n-Selectivity
Schlatzer, Thomas,Schr?der, Hilmar,Trobe, Melanie,Lembacher-Fadum, Christian,Stangl, Simon,Schl?gl, Christoph,Weber, Hansj?rg,Breinbauer, Rolf
supporting information, p. 331 - 336 (2019/11/16)
The Pd-catalyzed S-allylation of thiols with stable allylcarbonate and allylacetate reagents offers several advantages over established reactions for the formation of thioethers. We could demonstrate that Pd/BIPHEPHOS is a catalyst system which allows the transition metal-catalyzed S-allylation of thiols with excellent n-regioselectivity. Mechanistic studies showed that this reaction is reversible under the applied reaction conditions. The excellent functional group tolerance of this transformation was demonstrated with a broad variety of thiol nucleophiles (18 examples) and allyl substrates (9 examples), and could even be applied for the late-stage diversification of cephalosporins, which might find application in the synthesis of new antibiotics. (Figure presented.).
Reactions of 2-(α-Haloalkyl)thiiranes with nucleophilic reagents: V.* Reactions of 2-(α-chloroalkyl)thiiranes with organolithium compounds
Tomashevskii,Sokolov,Potekhin
experimental part, p. 1822 - 1825 (2011/04/17)
2-(α-Haloalkyl)thiiranes reacted with methyl-, butyl-, and phenyllithium to give the corresponding allyl sulfides. The reactions of diastereoisomeric erythro-and threo-2-(1-chloroethyl)thiiranes with phenyllithium were stereospecific, and they afforded (E)-and (Z)-1-phenylsulfanylbut-2-enes, respectively. 3-Chloromethyl-2,2- dimethylthiirane and phenyllithium gave rise to a mixture of 3-methyl-3-phenylsulfanylbut-1-ene and 3-methyl-1-phenylsulfanylbut-2-ene. The reactions of 2-chloromethylthiiranes with phenyllithium and methyllithium in the presence of a catalytic amount of copper(I) iodide (10 mol %) led to the formation of substituted thiiranes as the major products. Mechanisms of the observed transformations are discussed. Pleiades Publishing, Ltd., 2010.
Fast ruthenium-catalysed allylation of thiols by using allyl alcohols as substrates
Zaitsev, Alexey B.,Caldwell, Helen F.,Pregosin, Paul S.,Veiros, Luis F.
scheme or table, p. 6468 - 6477 (2010/02/28)
The allylation of aromatic and aliphatic thiols, by using allyl alcohols as substrates, requires only minutes at ambient temperature with either a Ru Iv catalyst, [Ru(Cp*)(n3CH5)(CH 3CN)2](PF6)2 (2; Cp* = pentamethylcyclopentadienyl) or a combination of [Ru(Cp*)(CH 3CN)3](PF6) and camphor sulfonic acid. Quantitative conversion is normal and the catalyst possesses high functional-group tolerance. The use of [Ru(Cp*)(CH3CN) 3](PF6) alone affords poor results. A comparison is made to the results from catalytic runs based on the use of carbonates rather than alcohols, by using 2 as the catalyst, and it is shown that the products from the alcohols are formed faster, so there is no advantage in using a carbonate substrate. The observed branched-to-linear (b/1) ratios when using substituted alcohols decrease with time suggesting that the catalysts isomerise the products. A new methodology from which one can select the desired isomeric product is proposed. DFT calculations and NMR spectroscopic measurements, by using an arene sulfonic acid as co-catalyst, suggest that 6-complexes are not relevant for the catalytic system. Moreover, the DFT results indicate that l)any rf-complexes from the acids RC6H4SO 3H result from deprotonation of the acid, 2) complexation of the thiol, via the deprotonated sulfur atom, is preferred over complexation of the O atom of the sulfonate, RC6H4SO3and 3) a sulfonate O-atom complex will be difficult to detect.
Mechanical stirring speed in water/hexane biphasic catalyst controls regioselectivity of Pd-catalyzed allylation reaction
Komiya, Sanshiro,Sako, Akari,Kosuge, Hirofumi,Hirano, Masafumi,Komine, Nobuyuki
, p. 640 - 641 (2008/12/21)
Vigorous mechanical mixing of the water/hexane biphasic Pd-catalyzed allylation of benzenethiol gave sterically congested allyl sulfides, due to high reactivity of the enforced orientation of the η1-allylpalladium intermediate at the solvent in
Selective allylation of arenethiols using water-soluble palladium complex catalyst in recyclable water/hexane biphasic media
Komine, Nobuyuki,Sako, Akari,Hirahara, Shin-Ya,Hirano, Masafumi,Komiya, Sanshiro
, p. 246 - 247 (2007/10/03)
Allylation of arenethiols by allylic alcohol with sterically hindered carbon of the allylic moiety is smoothly catalyzed by Pd(OAc)2/TPPTS in biphasic water/hexane media under ambient conditions. The catalyst water layer can be repeatedly reuse
The Formation of Allyl Sulphides by Phenylthio-migration: Control by Silicon
Fleming, Ian,Paterson, Ian,Pearce, Andrew
, p. 256 - 262 (2007/10/02)
When γ-silyl-β-phenylthio-alcohols are treated with acid, the strategically placed silyl group encourages the rearrangement of the phenylthio-group, both from a secondary migration origin to a secondary migration terminus, and from a secondary migration origin to a tertiary migration terminus (4)->(6).Geraniol/nerol (12) and linalool (14) have been synthesised from a common intermediate (11) using this type of reaction.Phenylthio-migration from a tertiary migration origin (17)->(3) can be controlled to a limited extent by a suitably placed silyl group, but it is easier to achieve direct β-elimination of the silyl and phenylthio-groups (17)->(18).
Formation of Allyl and Cyclopropylcarbinyl Sulphides in the Regiospecific Reactions of Arenesulphenyl Chlorides with Allyl- and But-3-enyl-cobaloximes
Ashcroft, Martyn R.,Gupta, B. Dass,Johnson, Michael D.
, p. 2021 - 2025 (2007/10/02)
Allyl- and substituted-allyl-bis(dimethylglyoximato)pyridinecobalt(III) complexes react regiospecifically with 2,4-dinitrobenzenesulphenyl chloride to give moderate (30-45percent) yields of the corresponding rearranged allyl 2,4-dinitrophenyl sulphides.The corresponding rearranged allyl derivative of the dimethylglyoxime is a major by-product.But-3-enylbis(dimethylglyoximato)pyridinecobalt(III) complexes also react regiospecifically to give cyclopropylmethyl 2,4-dinitrophenyl sulphides.The reactions are interpreted in terms of an electrophilic attack of the sulphur on the γ- and δ-carbon of the allyl- or butenyl-ligand, respectively, with concurrent or subsequent loss of cobaloxime(III), and with concurrent or subsequent cyclisation of the organic ligand in the case of the butenyl complexes.Benzenesulphenyl bromide and chloride react much more slowly and their reaction with allylbis(dimethylglyoximato)pyridinecobalt(III) has been briefly explored.
