Indium(iii) catalysed substrate selective hydrothiolation of terminal alkynes

Sarma, Rupam; Rajesh, Nimmakuri; Prajapati, Dipak

doi:10.1039/c2cc30350g

Cited by 60 publications

(21 citation statements)

References 38 publications

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“…Interestingly, catalytic reactions are known to mostly lead to the formation of mono‐addition products, consistent with Markovnikov’s rule, whereas radical‐type reactions tend to favor the formation of 1,2‐double‐addition products. However, Prajapati and co‐workers reported the reaction between aromatic and aliphatic thiols with alkynes in the presence of In(OTf) 3 leading to ( E )‐vinyl sulfides 26. We drew similar conclusions.…”

Section: Methodssupporting

confidence: 66%

Highly Selective Hydrothiolation of Unsaturated Organosilicon Compounds Catalyzed by Scandium(III) Triflate

Kuciński

Pawluć

Marciniec

et al. 2015

Chemistry A European J

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The first use of a Lewis acid catalyst in the addition reaction of both aromatic and aliphatic thiols to unsaturated organosilicon compounds is reported. In catalytic tests, scandium(III) triflate demonstrates high catalytic activity in this process. Under mild conditions (25 °C, room temperature, 1-10 h) a number of thioether-functionalized organosilicon species are obtained with appreciable selectivity. This study constitutes the first example of allylsilane hydrothiolation that gives the Markovnikov regioisomer as the main product. Ethynylsilanes are also successfully used in the hydrothiolation reaction in the presence of Sc(OTf)3 .

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Section: Methodssupporting

confidence: 66%

Highly Selective Hydrothiolation of Unsaturated Organosilicon Compounds Catalyzed by Scandium(III) Triflate

Kuciński

Pawluć

Marciniec

et al. 2015

Chemistry A European J

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“…Another example of regioselectivity control has been recently shown using catalytic amounts of In(OTf) 3 . Addition of heteroaromatic thiols to arylacetylenes proceeded in a Markovnikov‐type fashion leading to vinyl sulfides 6 in good yields 80–90 % (Scheme ), while aliphatic and aromatic thiols formed linear products 7 ( E / Z >5:1).…”

Section: Formation Of Monofunctionalized Akenes (Vinyl Chalcogenides)mentioning

confidence: 99%

“…Another example of regioselectivity control has been recently shown using catalytic amountso fI n(OTf) 3 . [34] Addition of heteroaromatic thiols to arylacetylenesp roceeded in aM arkovnikov-type fashion leadingt ov inyl sulfides 6 in good yields 80-90 %( Scheme 16), while aliphatic and aromatic thiols formed linear products 7 (E/Z > 5:1). Though no mechanistic investigations have been performed in this communication, it was assumed that depending on the thiol nucleophilicity, In(OTf) 3 may interact either with an alkyne to form acetylenide or with at hiol to form sulfide, thus leading to linear or branched products.…”

Section: Catalytic Systems Leadingt Om Arkovnikov-type (Branched)vinymentioning

confidence: 99%

Metal Catalysis in Thiolation and Selenation Reactions of Alkynes Leading to Chalcogen-Substituted Alkenes and Dienes

Orlov

2015

ChemistryOpen

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This review covers recent achievements in metal‐catalyzed Z−H and Z−Z (Z=S, Se) bond addition to the triple bonds of alkynes—a convenient and atom‐efficient way to carbon‐element bond formation. Various catalytic systems (both homogeneous and heterogeneous) developed to date to obtain mono‐ and bis‐chalcogen‐substituted alkenes or dienes, as well as carbonyl compounds or heterocycles, starting from simple and available alkynes and chalcogenols or dichalcogenides are described. The right choice of metal and ligands allows us to perform these transformations with high selectivities under mild reaction conditions, thus tolerating unprotected functional groups in substrates and broadening ways of further modification of the products. The main aim of the review is to show the potential of the catalytic methods developed in synthetic organic chemistry. Thus, emphasis is made on the scope of reactions, types of products that can be selectively formed, convenience, and scalability of the catalytic procedures. A brief mechanistic description is also given to introduce new readers to the topic.

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“…Thus, in 2012 Prajapati and co‐workers considered the importance of developing methods that used a single catalyst for different fundamental transformations in a single reaction flask 28. Based on this concept, they reported on the use of indium(III) triflate to catalyze both Markovnikov and anti‐Markovnikov hydrothiolation of terminal alkynes just by variation of the nature of the thiol employed 29. In particular, these studies revealed that heteroaromatic thiols Het‐SH (Het = benzothiazole, benzooxazole, thiazoline, pyridine) added selectively to aryl acetylenes in a Markovnikov fashion to give branched vinyl sulfides [Equation (6)], whereas aromatic and aliphatic thiols added to phenylacetylene in an anti‐Markovnikov way under the same conditions to afford mixtures of E and Z linear isomers with net prevalence of the former [Equation (7)].…”

Section: Metal‐catalyzed Hydrothiolation – Regioselectivity and Sterementioning

confidence: 99%

Metal‐Catalyzed and Metal‐Free Alkyne Hydrothiolation: Synthetic Aspects and Application Trends

Dondoni

Marra

2014

Eur J Org Chem

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Alkyne hydrothiolation – that is, the addition of the SH bond of a thiol across the carbon‐carbon triple bond of an unactivated alkyne – belongs to the ample class of hydrofunctionalization reactions whose main feature is their occurrence with total atom economy. Hence this reaction is emerging as a valuable tool for the preparation of sulfur‐containing compounds such as vinyl thioethers, which are of interest for their own biological properties and for their use as intermediates in total synthesis. Thus, the first part of this review deals with the various efforts directed towards the preparation of vinyl thioethers in a regio‐ and diastereoselective manner by metal‐catalyzed approaches in recent years. The number of methods employed, with use of a variety of catalysts and reaction conditions, allow the synthesis of vinyl thioethers to be carried out with high efficiency and selectivity. The second part of the article is based on the use of the photoinduced free‐radical approach to hydrothiolation, which allows the introduction of two thiol fragments across the carbon‐carbon triple bond, thereby leading to the formation of dithioethers. This approach turned out to be especially useful as a ligation tool for the installation of densely functionalized arrays on various scaffolds and complex biomolecular systems. Concluding remarks emphasize the role of the photoinduced free‐radical strategy as a complementary tool to copper‐catalyzed azide‐alkyne cycloaddition.

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Indium(iii) catalysed substrate selective hydrothiolation of terminal alkynes

Abstract: In(OTf)(3) is reported as the first catalyst having the ability to selectively catalyse both Markovnikov and anti-Markovnikov hydrothiolation of terminal alkynes under identical reaction conditions depending upon the nature of the thiol employed.

Cited by 60 publications

References 38 publications

Highly Selective Hydrothiolation of Unsaturated Organosilicon Compounds Catalyzed by Scandium(III) Triflate

Highly Selective Hydrothiolation of Unsaturated Organosilicon Compounds Catalyzed by Scandium(III) Triflate

Metal Catalysis in Thiolation and Selenation Reactions of Alkynes Leading to Chalcogen-Substituted Alkenes and Dienes

Metal‐Catalyzed and Metal‐Free Alkyne Hydrothiolation: Synthetic Aspects and Application Trends

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