Recent developments on 1,2-difunctionalization and hydrofunctionalization of unactivated alkenes and alkynes involving C–S bond formation

Dong, Bi‐Cheng; Shen, Jian; Xie, Lan‐Gui

doi:10.1039/d2qo01699k

Cited by 52 publications

(26 citation statements)

References 131 publications

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“…For better understanding, the review is categorized according to the mode of reactions viz , (i) C−S bond formation via difunctionalization of alkenes and alkynes, (ii) C−S bond formation via C−H functionalization, and (iii) C−S bond formation via radical cyclization. Though the fragmental aspects of the photochemical C−S bond formation strategy are explained in some of the reviews, this review presents some recent advances in visible‐light driven C−S bond formation [10e–i] …”

Section: Introductionmentioning

confidence: 99%

Metal‐Free Visible‐light Mediated C−S Bond Formation

Sahoo,

Barik,

Dam

et al. 2023

Asian J Org Chem

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The upsurge in interest in the development of methodologies for the synthesis of sulfur‐containing compounds via the use of visible‐light has been established as a sustainable tool in organic chemistry. Particularly, visible‐light mediated C−S bond formation has gained popularity due to its operational simplicity, minimized by‐products, easy handling, mild reaction conditions, etc. Photochemistry not only provides a sustainable way to synthesize complex molecules but also has the ability to overcome many challenges which are difficult to attain by conventional thermal pathways. Owing to the biological importance of sulfur‐containing compounds, the present review focused on the C−S bond formation under metal‐free conditions mediated by visible‐light. The objective of the current review is to bring out the unearthing collection regarding C−S bond formation via photoredox catalysis. For better understanding, the review is categorized according to the mode of reactions viz, C−S bond formation via difunctionalization of alkenes and alkynes, C−S bond formation via C−H functionalization, and C−S bond formation via radical cyclization. All the reactions in each of the sections are described with selected examples with a proper explanation of the proposed mechanism.

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Section: Introductionmentioning

confidence: 99%

Metal‐Free Visible‐light Mediated C−S Bond Formation

Sahoo,

Barik,

Dam

et al. 2023

Asian J Org Chem

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“…Radical addition, coupling, rearrangement, and cleavage reactions are powerful in the synthesis of diverse molecular structures [ 1 , 2 ]. Difunctionalization reactions initiated with radical addition are attractive for both synthetic efficiency and product diversity considerations [ 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 ]. We have recently reported radical 1,2-difunctionalization ( Scheme 1 I) [ 13 ] and addition-/cyclization-based difunctionalization reactions ( Scheme 1 II) [ 14 ].…”

Section: Introductionmentioning

confidence: 99%

Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions

Zhang

2023

Molecules

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Radical transformations are powerful in organic synthesis for the construction of molecular scaffolds and introduction of functional groups. In radical difunctionalization reactions, the radicals in the first functionalized intermediates can be relocated through resonance, hydrogen atom or group transfer, and ring opening. The resulting radical intermediates can undertake the following paths for the second functionalization: (1) couple with other radical groups, (2) oxidize to cations and then react with nucleophiles, (3) reduce to anions and then react with electrophiles, (4) couple with metal-complexes. The rearrangements of radicals provide the opportunity for the synthesis of 1,3-, 1,4-, 1,5-, 1,6-, and 1,7-difunctionalization products. Multiple ways to initiate the radical reaction coupling with intermediate radical rearrangements make the radical reactions good for difunctionalization at the remote positions. These reactions offer the advantages of synthetic efficiency, operation simplicity, and product diversity.

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“…In our recent studies, 10 we found that thiirenium ion intermediates, formed by the electrophilic activation of terminal alkynes with dimethyl(methylthio)sulfonium trifluoromethanesulfonate (DMTSM), could be intercepted by triflate ( − OTf) immediately in a Markovnikov manner. 11 Pioneering studies showed that the nucleophilicity of the reagent employed in the ring-opening addition to the thiirenium ion would have significant impact on the regioselectivity.…”

Section: Introductionmentioning

confidence: 99%