An oxidative cross-coupling reaction of 4-hydroxydithiocoumarin and amines/thiols using a combination of I<sub>2</sub> and TBHP: access to lead molecules for biomedical applications

Mahato, Karuna; Arora, Neha; Bagdi, Prasanta Ray; Gattu, Radhakrishna; Ghosh, Siddhartha Sankar; Khan, Abu T.

doi:10.1039/c7cc08502h

Cited by 26 publications

(15 citation statements)

References 31 publications

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“…First, performing the electrolysis of 4-fluorothiophenol (45) in the absence of N-Ts-4-methoxyaniline (2) delivered the corresponding homo-coupling product 46 in 95% yield (Figure 4A). Second, using disulfide intermediate 46 as the cross-coupling partner to replace 4-fluorothiophenol (45) to react with N-Ts-4-methoxyaniline (2), the corresponding alternating current electrolysis occurred smoothly and led to desired cross-coupling product 5 in 74% yield (Figure 4B). These results suggest that disulfide might be the key intermediate for N-S bond formation.…”

Section: Resultsmentioning

confidence: 99%

“…The reactions between 4-fluorothiophenol (45) and N-Ts-4-methoxyaniline (2) with different reaction times were next conducted. As shown in Figure 5, performing the electrolysis with an output voltage of 5 V for 2.5 h, product 5 could not be detected.…”

Section: Resultsmentioning

confidence: 99%

“…[34][35][36][37][38][39][40] Over the past decades, methods for N-S bonds containing compounds synthesis have been largely developed. [41][42][43][44][45][46][47][48][49][50] Although the nucleophilic substitution of amines with various sulfenylation reagents is proved the most classical method (Figure 2B, top), most of these reactions require additional processes to synthesize sulfenylation reagents that often lead to large amounts of undesired by-products. Oxidative cross-coupling of commercially available thiophenols/thiols with amines has emerged as an increasingly popular method for N-S bond formation (Figure 2B, bottom).…”

Section: (B) Previous Methods For N-s Bonds Formation (C) Our Design For N-s Bonds Formationmentioning

confidence: 99%

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Radical–Radical Cross-Coupling Assisted N–S Bond Formation Using Alternating Current Protocol

Yuan

Wang

et al. 2022

CCS Chem

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Alternating current (AC) electrolysis is a promising, yet challenging, and under-developed protocol in organic synthesis. To achieve as high atom-efficiency as possible and avoid the use of external oxidant, the electrochemistry has become a standard organic synthesis tool. Herein, AC-based protocol is a superior option than its counterpart (DC: direct current), especially for those reactions that cannot be accomplished by DC.With an aim to achieve this objective, we have employed the AC electrolysis successfully to deliver the unprecedented cross-coupling of sulfonyl or acyl substituted aniline derivatives with thiophenols/thiols under exogenous-oxidant-and catalyst-free conditions. Numerous N-S bonds containing compounds (Total 40 number) have been prepared in up to 93% yield and good selectivity. Interestingly, no reactivity has been noted using DC electrolysis or traditional chemical approaches under our reaction conditions. Mechanistic studies indicated that disulfide is the key intermediate in this alternating current mediated radical-radical crosscoupling reaction. Therefore, the current work does not only provide an efficient method for N-S bonds formation, but also pave new sustainable avenues to innovation in organic synthesis.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: (B) Previous Methods For N-s Bonds Formation (C) Our Design For N-s Bonds Formationmentioning

confidence: 99%

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Radical–Radical Cross-Coupling Assisted N–S Bond Formation Using Alternating Current Protocol

Yuan

Wang

et al. 2022

CCS Chem

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“…Subsequently,Khan's group also reported an iodine/TBHP-induced synthesis of sulfenamides 161 through the formation of novel SÀN, SÀCa nd SÀSb onds from 4-hydroxy-dithiocoumarin 158 and amines 159 or thiols 160 (Scheme 51). [127] In the reaction, it showed ag ood tolerance with variouso fs econdary amines and afforded the desired products in relatively good yields. Notably,t he four compounds, 159 a, 159 b, 159 c and 159 d,h ave exhibited antiproliferativea ctivity against the breast cancerc ell line MCF7, and may be al ead molecule for future drug development.…”

Section: Iodine-promoted Thiolation Of Sp 3 Càhb Ondmentioning

confidence: 95%

Recent Advances in Iodine‐Promoted C−S/N−S Bonds Formation

Zhang

Wang

Jiang

et al. 2020

Chemistry A European J

111

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Sulfur-containing scaffold, as aubiquitous structural motif, has been frequently used in natural products, bioactive chemicals and pharmaceuticals, particularly CÀS/NÀS bonds are indispensable in many biological importantc ompounds and pharmaceuticals. Development of mild and general methods for CÀS/NÀSb onds formation hasg reat significance in modern research. Iodine and its derivativesh ave been recognizeda si nexpensive,e nvironmentally benign and easy-handled catalysts or reagents to promote the construction of CÀS/NÀSb onds under mild reactionc onditions, with good regioselectivities andb road substrate scope.E specially based on this, severaln ew strategies, such as oxidation relay strategy,havebeen greatlydeveloped and accelerated the advancement of this field. This review focuses on recent advances in iodine and its derivatives promoted hybridized CÀS/NÀSbonds formation.The features and mechanisms of corresponding reactions are summarized and the results of some cases are compared with those of previous reports. In addition, the future of this domain is discussed.

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“…A method for the S ‐functionalization of 4‐hydroxydithiocoumarins 116 was developed: the corresponding sulfenamides 118 are formed through the action of the I 2 /TBHP system in DMF (Scheme ) . Both aliphatic amines and anilines 117 successfully participate in this reaction, but when annulated aromatic amines 117′ are used only the C ‐thiolation products 119 are formed.…”

Section: Synthesis Of Sulfenamides and Sulfinamidesmentioning

confidence: 99%

Oxidative Coupling with S–N Bond Formation

2018

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Oxidative strategies are a powerful tool in organic synthesis for the formation of heteroatom–heteroatom, carbon–heteroatom, and carbon–carbon bonds. Among these processes the reactions of oxidative S–N bond formation deserve considerable interest as convenient, effective, and environmentally friendly alternatives to existing methods for the synthesis of a great variety of organic compounds widely used in organic and medicinal chemistry. These transformations take place through the interaction of S‐ and N‐reagents and an oxidant, by radical or ionic mechanisms. Sulfinic acids and their salts, thiols, sulfonyl hydrazides, and thiosulfonates are generally used as S‐reagents; aliphatic and aromatic amines are usually applied as N‐reagents. The role of the oxidant mostly lies in the oxidation of the S‐reagent, after which the formed active species reacts with the N‐reagent to result in the S–N coupling product. There are two versions of oxidative S–N coupling processes: the intermolecular variant opens simple pathways to sulfen‐, sulfin‐, and sulfonamides, sulfenyl‐ and sulfoximines, sulfanes, and sulfur diimides, whereas the intramolecular one leads to the formation of various heterocycles. Of the major problems associated with successful performance of oxidative S–N coupling reactions, the first relates to the search for coupling partners that will work together to form a new bond under oxidative conditions. The second is the choice of a suitable oxidative system that will not overoxidize starting compounds. That is why mild oxidants, such as hypervalent iodine compounds and copper salts and complexes, are generally applied in these processes. This is the first exhaustive review relating to achievements in oxidative transformations involving S–N bond formation. It summarizes 134 references, mainly from 2000 to 2018, and is divided into chapters according to the classes of compounds synthesized.

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An oxidative cross-coupling reaction of 4-hydroxydithiocoumarin and amines/thiols using a combination of I₂ and TBHP: access to lead molecules for biomedical applications

Cited by 26 publications

References 31 publications

Radical–Radical Cross-Coupling Assisted N–S Bond Formation Using Alternating Current Protocol

Radical–Radical Cross-Coupling Assisted N–S Bond Formation Using Alternating Current Protocol

Recent Advances in Iodine‐Promoted C−S/N−S Bonds Formation

Oxidative Coupling with S–N Bond Formation

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An oxidative cross-coupling reaction of 4-hydroxydithiocoumarin and amines/thiols using a combination of I2 and TBHP: access to lead molecules for biomedical applications

Cited by 26 publications

References 31 publications

Radical–Radical Cross-Coupling Assisted N–S Bond Formation Using Alternating Current Protocol

Radical–Radical Cross-Coupling Assisted N–S Bond Formation Using Alternating Current Protocol

Recent Advances in Iodine‐Promoted C−S/N−S Bonds Formation

Oxidative Coupling with S–N Bond Formation

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Product

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An oxidative cross-coupling reaction of 4-hydroxydithiocoumarin and amines/thiols using a combination of I₂ and TBHP: access to lead molecules for biomedical applications