New and Facile Synthesis of Thiosulfonates from Sulfinate/Disulfide/I2 System

Fujiki, Kiyoko; Tanifuji, Naoki; Sasaki, Yohei; Yokoyama, Taku

doi:10.1055/s-2002-20031

Cited by 85 publications

(42 citation statements)

References 6 publications

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“…The organomagnesium species of 1 b could also be quenched with iodine and crosscoupled with 2-phenylethynylzinc chloride or 1-pentynylzinc chloride to give sulfoxides 3 h and 3 i in 94 and 74 % yield, respectively ( Table 1, entries 8 and 9). Likewise, tosyl (Tos) cyanide or (S)-(4-chlorophenyl)benzene thiosulfonate [17] were used to quench the magnesiated derivative of 1 b to give nitrile 3 j and thioether 3 k in 79 and 82 % yield, respectively (Table 1, entries 10 and 11). Using similar procedures, we were able to functionalise the diaryl sulfoxides 1 c (FG = CO 2 tBu), 1 d (FG = CN), 1 e (FG = CF 3 ) and 1 f (FG = trimethylsilyl (TMS)-acetylene) in 61-91 % yield ( Table 1, entries 12-18).…”

Section: Resultsmentioning

confidence: 99%

Difunctionalisation of Arenes and Heteroarenes by Directed Metallation and Sulfoxide–Magnesium Exchange

Melzig

Rauhut

Naredi‐Rainer

et al. 2011

Chemistry A European J

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The aryl sulfoxide moiety allows an expedient two-step difunctionalisation of readily available diaryl sulfoxides. Highly functionalised 1,2,4-trisubstituted arenes and difunctionalised heteroarenes (furans, thiophenes, benzofurans and pyridines) were prepared in a two-step sequence, triggered by an aryl sulfoxide group. In the first step, the sulfoxide moiety acts as a metallation-directing group, allowing smooth ortho-magnesiation with TMPMgCl⋅LiCl (TMP=tetramethylpiperidine). After a quenching reaction with an electrophile, the resulting sulfoxide is converted into a second magnesium reagent with iPrMgCl⋅LiCl (sulfoxide-magnesium exchange), which can be trapped with various electrophiles. Highly chemoselective TMPMgCl⋅LiCl and iPrMgCl⋅LiCl are compatible with a broad range of functional groups (e.g., F, Cl, CF(3) , CN, CO(2) tBu, alkynyl, ethers, thioethers). Large-scale reactions (25-40 mmol) and the preparation of fully functionalised furans and thiophenes are also reported.

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Section: Resultsmentioning

confidence: 99%

Difunctionalisation of Arenes and Heteroarenes by Directed Metallation and Sulfoxide–Magnesium Exchange

Melzig

Rauhut

Naredi‐Rainer

et al. 2011

Chemistry A European J

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“…Its copper(I)-mediated reaction with 4-chlorobenzoyl chloride, as a representative acid chloride, led to the benzylic ketone 16 b in 82 % yield (Scheme 7). Further electrophiles, such as ethyl (2-bromomethyl)acrylate [21] and (S)-(4-chlorophenyl)-benzenethiosulfonate, [27] furnished the corresponding products 16 c, d in yields of 67-75 % (entries 2 and 3, Table 3). Negishi cross-coupling reaction of 13 b with 4-iodoanisole using PEPPSI-IPr [16e-g] (0.25 mol %) as catalyst led to the expected product 16 e in 78 % yield (entry 4).…”

Section: Resultsmentioning

confidence: 99%

Preparation of Polyfunctional Arylmagnesium, Arylzinc, and Benzylic Zinc Reagents by Using Magnesium in the Presence of LiCl

Piller

Metzger

Schade

et al. 2009

Chemistry A European J

174

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The presence of LiCl considerably facilitates the insertion of magnesium into various aromatic and heterocyclic bromides. Several functional groups, such as -OBoc, -OTs, -Cl, -F, -CF(3), -OMe, -NMe(2), and -N(2)NR(2), are well tolerated. The presence of a cyano group leads in some cases to competitive reduction of the organic halide to the corresponding ArH compound. The presence of sensitive groups such as methyl or ethyl ester is tolerated upon in situ trapping of the intermediate magnesium reagent with ZnCl(2). This method can also be applied to the preparation of functionalized benzylic zinc reagents from benzylic chlorides. In the case of di- or tribromoaryl derivatives, directing groups such as -OPiv, -OTs, -N(2)NR(2), or -OAc orient the zinc insertion (Zn/LiCl) to the ortho-position, while the reaction with Mg/LiCl or Mg/LiCl/ZnCl(2) leads to regioselective insertion into the para-carbon-bromine bond. Large-scale experiments (20-100 mmol) for all of the metalation procedures are described.

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“…Although unsymmetrical S ‐alkyl methanethiosulfonates ( 7 ) are formed in high yield in a preferred solvent, the stoichiometric amount of toxic silver waste is not beneficial in terms of the green credentials of this method. The groups of Langlois and Fujiki employed bromine (route 2) or iodine (route 3) for the activation of the disulfide bond resulting in a lower PMI. Unfortunately, reactions were performed in hazardous dichloromethane.…”

Section: Thiosulfonate Synthesismentioning

confidence: 99%

Thiosulfonates as Emerging Reactants: Synthesis and Applications

et al. 2019

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The synthetic strategies towards thiosulfonates (RSO2SR1) are comprehensively reviewed from their original discovery to recent advances. Incorporation of the green credentials of the synthetic procedures towards thiosulfonates allows one to judge the merits of the state of the art, beyond the typical yield of a product and availability of the reactants. As reactant for organic transformations, thiosulfonates are particularly interesting given their possibility to react with nucleophiles, electrophiles and radicals. This review aims to give researchers, not familiar with the field, a good understanding of the general applications of thiosulfonates, while not skipping the recent important advances. The related, but less explored, selenosulfonates (RSO2SeR1) are also covered.

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New and Facile Synthesis of Thiosulfonates from Sulfinate/Disulfide/I2 System

Abstract: Thiosulfonates were prepared by the iodine oxidative sulfenylation of sulfinates with various disulfides in good yields both in the presence and absence of solvent. One of the important biological applications of sulfenylation is the reaction of cyclic disulfides.

Cited by 85 publications

References 6 publications

Difunctionalisation of Arenes and Heteroarenes by Directed Metallation and Sulfoxide–Magnesium Exchange

Difunctionalisation of Arenes and Heteroarenes by Directed Metallation and Sulfoxide–Magnesium Exchange

Preparation of Polyfunctional Arylmagnesium, Arylzinc, and Benzylic Zinc Reagents by Using Magnesium in the Presence of LiCl

Thiosulfonates as Emerging Reactants: Synthesis and Applications

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