A radical-chain reaction of isocyanides with selenosulfonates and water: facile synthesis of selenocarbamates under metal-free conditions

Fang, Yi; Liu, Can; Wang, Fei; Ding, Rao; Wang, Shun‐Yi; Ji, Shun‐Jun

doi:10.1039/c8qo01364k

Cited by 21 publications

(10 citation statements)

References 38 publications

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“…Based on the above results and a previous report, we depict a plausible mechanism involving the radical process (see Scheme ). By interaction with 1a , the homolysis of selenosulfonate 2a will occur in the mixture to give benzenesulfonyl radical A and selenium radical B .…”

supporting

confidence: 55%

“…Recently, our group reported the preparation of secondary selenocarbamates through radical-chain reactions of isocyanides, selenosulfonates and water under metal-free conditions (Scheme A) . Inspired by this work and in continuation of our work on organoselenium chemistry, we herein report a new method for the construction of N -(carboselenoate) benzimidazolones via reactions of o -diisocyanoarenes with selenosulfonates (Scheme B).…”

mentioning

confidence: 97%

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Metal-Free Synthesis of N-(Carboselenoate) Benzimidazolones by Cascade Cyclization of ortho-Diisocyanoarenes and Selenosulfonates

et al. 2019

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confidence: 55%

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confidence: 97%

Metal-Free Synthesis of N-(Carboselenoate) Benzimidazolones by Cascade Cyclization of ortho-Diisocyanoarenes and Selenosulfonates

et al. 2019

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“…Due to their unique structures and reactivities, isocyanides are versatile C1 synthons in the synthesis of nitrogen-containing compounds . By merging isocyanides, selenosulfonates, and water, a set of secondary selenocarbamates 157 - 3 were furnished by Ji and co-workers (Scheme A) . On the other hand, isocyanide insertion reactions enable the facile construction of heterocycles .…”

Section: Radical-mediated Desulfonylation Of Thio/selenosulfonates Vi...mentioning

confidence: 99%

“…558 By merging isocyanides, selenosulfonates, and water, a set of secondary selenocarbamates 157-3 were furnished by Ji and co-workers (Scheme 157A). 559 On the other hand, isocyanide insertion reactions enable the facile construction of heterocycles. 326 By virtue of the ortho-diisocyanoarenes 157-4 as substrates, this radical-chain protocol was further applied to metal-free synthesis of N-(carboselenoate) benzimidazolones 157-5, boosting its practicality (Scheme 157B).…”

Section: Desulfonylative Thiolation and Selenylationmentioning

confidence: 99%

Desulfonylation via Radical Process: Recent Developments in Organic Synthesis

et al. 2021

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As the "chemical chameleon", sulfonyl-containing compounds and their variants have been merged with various types of reactions for the efficient construction of diverse molecular architectures by taking advantage of their incredible reactive flexibility. Currently, their involvement in radical transformations, in which the sulfonyl group typically acts as a leaving group via selective C−S, N−S, O−S, S−S, and Se−S bond cleavage/ functionalization, has facilitated new bond formation strategies which are complementary to classical two-electron cross-couplings via organometallic or ionic intermediates. Considering the great influence and synthetic potential of these novel avenues, we summarize recent advances in this rapidly expanding area by discussing the reaction designs, substrate scopes, mechanistic studies, and their limitations, outlining the state-of-the-art processes involved in radical-mediated desulfonylation and related transformations. With a specific emphasis on their synthetic applications, we believe this review will be useful for medicinal and synthetic organic chemists who are interested in radical chemistry and radical-mediated desulfonylation in particular. CONTENTS

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“…100 In 2019, Fang and co-workers developed a facile synthetic strategy for preparing secondary selenocarbamates derivatives 131 in moderate to high yields via metal-free 3-CRs of isocyanide 1, selenosulfonate 130, and water under mild conditions (Scheme 37). 101 They proposed a radical-chain process to illuminate the mechanism for the generation of secondary selenocarbamates. As shown in the mechanism in Scheme 37, benzenesulfonyl radical 132 and selenium radical 133 were formed by the homolysis of selenosulfonate 130a.…”

Section: ■ Other Reactionsmentioning

confidence: 99%

Sustainable Synthesis of Pseudopeptides via Isocyanide-Based Multicomponent Reactions in Water

Nazeri

Nasiriani

Farhid

et al. 2022

ACS Sustainable Chem. Eng.

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The impressive success in the synthesis of novel products via sustainable and green methods is a crucial purpose in organic synthesis. Water as a “green solvent” plays a vital role in accelerating some organic reactions, displaying unique reactivity and selectivity from conventional organic solvents. The isocyanide-based multicomponent reactions (I-MCRs) as sustainable and versatile reactions have received significant consideration in the synthesis of pseudopeptidic frames, especially in drug discovery. This is because of the unique nature of isocyanides that play as a special active reactant. I-MCRs in water as a solvent and reagent for the synthesis of pseudopeptidic compounds have become an interesting research direction, enabling simultaneous growth of both I-MCRs and green solvents toward ideal organic synthesis. The reaction rate of I-MCRs was accelerated in water as a solvent due to the lower activation volumes and condensation of several reactants into a single reactive intermediate and product. Furthermore, I-MCRs executed possibly in water are mild, easily controlled, and environmentally friendly, which conform well to “Green Chemistry” principles. On the other hand, these powerful organic syntheses in water and aqueous media are perpetuated by acceleration and reduction in the number of workups, purification, and extraction steps. The main subject of this review is I-MCRs that are performed in the water toward the sustainable synthesis of pseudopeptide structures. It deserves to be pointed out that whereas significant progress has been recently made on the MCRs in water and aqueous media for organic transformations, there is no exclusive account to focus on and publish about the eco-friendly I-MCRs for pseudopeptides. Nevertheless, we hope this themed assemblage will be attractive and useful for organic and pharmaceutical chemists and encourage more reaction development in this fascinating engaging field.

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A radical-chain reaction of isocyanides with selenosulfonates and water: facile synthesis of selenocarbamates under metal-free conditions

Abstract: A facile synthesis of secondary selenocarbamates through metal-free multicomponent reactions of isocyanides, selenosulfonates and water is reported here. The reaction is easy to handle and proceeds smoothly under mild conditions.

Cited by 21 publications

References 38 publications

Metal-Free Synthesis of N-(Carboselenoate) Benzimidazolones by Cascade Cyclization of ortho-Diisocyanoarenes and Selenosulfonates

Metal-Free Synthesis of N-(Carboselenoate) Benzimidazolones by Cascade Cyclization of ortho-Diisocyanoarenes and Selenosulfonates

Desulfonylation via Radical Process: Recent Developments in Organic Synthesis

Sustainable Synthesis of Pseudopeptides via Isocyanide-Based Multicomponent Reactions in Water

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