Tunable and Practical Synthesis of Thiosulfonates and Disulfides from Sulfonyl Chlorides in the Presence of Tetrabutylammonium Iodide

Zheng, Yong; Qing, Feng‐Ling; Huang, Yangen; Xu, Xiu‐Hua

doi:10.1002/adsc.201600633

Cited by 72 publications

(55 citation statements)

References 85 publications

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“…Many synthetic chemists devoted continuous efforts to explore synthetic strategies for the preparation of thiosulfonates, therefore a number of methods have been established (Scheme ). These included: (i) the direct oxidation of thiols or disulfides, (ii) the coupling of disulfides or thiols with sodium sulfonate, (iii) the reduction of sulfonyl chlorides, and (iv) the reaction of sulfonyl halides with other thiols or thiolates . Sulfonyl chlorides are an important class of organic compounds that have long been used as inexpensive and commercially available starting materials in organic synthesis, materials science, and medicinal chemistry .…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Thiosulfonates via CuI‐Catalyzed Reductive Coupling of Arenesulfonyl Chlorides Using Na₂SO₃ or NaHSO₃ as Reductants

2017

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Am ild and efficient methodf or the synthesis of thiosulfonates has been developed through aC uI-catalyzed reductivec oupling of arenesulfonyl chlorides using Na 2 SO 3 or NaHSO 3 as the terminal reductantu nder an itrogen atmosphere at room temperature. Ab road scope of thiosulfonates was obtained in high to excellent yields via this simple, practical and economical transformation.T he ease of handling, the use of low-costa nd readily available reaction materials at room temperature,a nd the efficiency on al arge scale, make this method attractive in both organic synthesis and industrial applications.Thiosulfonate derivatives have shown ab road spectrum of biological activities [1] and widespreada pplications in both polymer production and photographic processes. [2] Furthermore, they are powerful sulfenylating agentsi ns ynthetic organic chemistry. [3] As sulfenylating agents, they are more stable and easier to handle than sulfinyl chlorides, and reactf aster and are more efficient than disulfides. Although the synthetic importanceo ft hiosulfonates is known,t hey have not been extensively applied in organic synthesis and have been seldom used in industrial processes as sulfenylating agentsb ecause there had not been very economical and practical methods for synthesizing them.Many synthetic chemists devoted continuous efforts to explore synthetic strategies for the preparation of thiosulfonates, therefore an umber of methods have been established (Scheme 1). These included:( i) the direct oxidation of thiols or disulfides, [4] (ii)the coupling of disulfides or thiols with sodium sulfonate, [5,6] (iii)the reduction of sulfonyl chlorides, [7,8] and (iv) the reactiono fs ulfonyl halides with other thiols or thiolates. [9] Sulfonylc hlorides are an important class of organic compounds that have long been used as inexpensive and commercially available startingm aterials in organic synthesis, materials science, and medicinal chemistry. [10] Severale ffective methodsh ave been developed for the synthesis of symmetrical thiosulfonates by reducing sulfonyl chlorides with N,N-dimethyl hydrazine, [7a] potassium iodide in anhydrous acetone/ pyridine, [7b] acetyl-chloride-activated zinc, [7c] samarium powder in DMF, [7d] and tetrabutylammoniumi odide. [8] Although these strategies provided useful accesst os ubstituted symmetrical thiosulfonates, there are noticeable drawbacks associated with them, such as relatively strict andh arsh reactionc onditions, expensive and sensitive reductants,e xcessive requirementsf or acid or base additives and tediousw ork-up procedures. In the case of reactions involving reductantsa nd bases, such as the KI/acetone/pyridine system, anhydrous acetone, as well as large quantities of the KI reductant and pyridine, are needed, with the latter requiring 2.5 equiv (1 mL, 12.5 mmol) rather than ac atalytic amount, as reported in literature. [7b] Owing to the toxicityo fp yridine, its use as ab ase is no longerf avored in organic synthesis. Therefore, the development of mild, economic,env...

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Section: Methodsmentioning

confidence: 99%

Synthesis of Thiosulfonates via CuI‐Catalyzed Reductive Coupling of Arenesulfonyl Chlorides Using Na₂SO₃ or NaHSO₃ as Reductants

2017

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“…Finally, under the optimized conditions without the addition of sulfoximine 2a , sodium benzenesulfinate self‐coupling product 4 was obtained in 82 % yield, providing analytical data consistent with that previously reported (Scheme , Equ. c) . However, self‐coupling product 4 did not react with sulfoximine 2a to give target product 3a (Scheme , Equ.…”

Section: Figurementioning

confidence: 99%

“…c). [24] However, self-coupling product 4 did not react with sulfoximine 2a to give target product 3a (Scheme 2, Equ. d).…”

mentioning

confidence: 99%

I₂‐Catalyzed N‐Sulfonylation of Sulfoximines with Sulfinates in Water at Room Temperature

et al. 2020

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“…The authors also evaluated other solvents (acetonitrile, ethyl acetate or tetrahydrofuran), but selected dichloromethane as the superior solvent. In 2016 Huang disclosed an alternative reduction with tetrabutylammonium iodide in acetonitrile/acetone (5:1) at room temperature (route 8) . The lower PMI value, the high LD 50 value for tetrabutylammonium iodide (Table ), the use of an acceptable solvent and the high yield, even for heteroarenesulfonyl chlorides, make this one of the most attractive approaches for the reductive coupling of sulfonyl chlorides ( 6 ).…”

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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Tunable and Practical Synthesis of Thiosulfonates and Disulfides from Sulfonyl Chlorides in the Presence of Tetrabutylammonium Iodide

Cited by 72 publications

References 85 publications

Synthesis of Thiosulfonates via CuI‐Catalyzed Reductive Coupling of Arenesulfonyl Chlorides Using Na₂SO₃ or NaHSO₃ as Reductants

Synthesis of Thiosulfonates via CuI‐Catalyzed Reductive Coupling of Arenesulfonyl Chlorides Using Na₂SO₃ or NaHSO₃ as Reductants

I₂‐Catalyzed N‐Sulfonylation of Sulfoximines with Sulfinates in Water at Room Temperature

Thiosulfonates as Emerging Reactants: Synthesis and Applications

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Tunable and Practical Synthesis of Thiosulfonates and Disulfides from Sulfonyl Chlorides in the Presence of Tetrabutylammonium Iodide

Cited by 72 publications

References 85 publications

Synthesis of Thiosulfonates via CuI‐Catalyzed Reductive Coupling of Arenesulfonyl Chlorides Using Na2SO3 or NaHSO3 as Reductants

Synthesis of Thiosulfonates via CuI‐Catalyzed Reductive Coupling of Arenesulfonyl Chlorides Using Na2SO3 or NaHSO3 as Reductants

I2‐Catalyzed N‐Sulfonylation of Sulfoximines with Sulfinates in Water at Room Temperature

Thiosulfonates as Emerging Reactants: Synthesis and Applications

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Synthesis of Thiosulfonates via CuI‐Catalyzed Reductive Coupling of Arenesulfonyl Chlorides Using Na₂SO₃ or NaHSO₃ as Reductants

Synthesis of Thiosulfonates via CuI‐Catalyzed Reductive Coupling of Arenesulfonyl Chlorides Using Na₂SO₃ or NaHSO₃ as Reductants

I₂‐Catalyzed N‐Sulfonylation of Sulfoximines with Sulfinates in Water at Room Temperature