Synthesis of Thioethers. Amide Solvent-Promoted Nucleophilic Displacement of Halide by Thiolate Ion

Campbell, J. Robert

doi:10.1021/jo01030a039

Cited by 97 publications

(16 citation statements)

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“…The formation of CS bonds represents a key step in the synthesis of many important molecules that are of biological, pharmaceutical, and material interest 1. Generally, the generation of CS bonds, especially C aryl S bonds involved the coupling reaction,2 the S N Ar reaction3 and the electrophilic substitution reaction4 of activated aryl halides with arenethiols. Among them, the transition metal‐catalyzed C aryl S bond formation reactions by direct coupling of aryl halides and arenethiols have received much attention, and various metal catalysts such as Pd,5 Cu,6 and Fe7 etc.…”

Section: Methodsmentioning

confidence: 99%

A Highly Efficient Palladium‐Catalyzed One‐Pot Synthesis of Unsymmetrical Aryl Alkyl Thioethers under Mild Conditions in Water

Wang¹,

Zhou²,

Chen³

et al. 2012

Adv Synth Catal

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Section: Methodsmentioning

confidence: 99%

A Highly Efficient Palladium‐Catalyzed One‐Pot Synthesis of Unsymmetrical Aryl Alkyl Thioethers under Mild Conditions in Water

Wang¹,

Zhou²,

Chen³

et al. 2012

Adv Synth Catal

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“…-butylcyclohexane (from the commercially available alcohols with CH3S02C1 in ~y r i d i n e~~) with sodium thiophenolate (NaOCH3 + C6HsSH) in DMF. 35 The sulphides were oxidized with bromine36 to yield the sulphoxides lb-3b.…”

Section: Methodsmentioning

confidence: 99%

¹H, ¹³C, ¹⁷O and ³³S NMR investigation of some cyclohexyl phenyl sulphides, sulphoxides and sulphones

Duddeck

Korek

Rosenbaum

et al. 1986

Magnetic Reson in Chemistry

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The '€I and -C NMR signals of cyclohexyl phenyl sulphides, sulphoxides and sulphones were almost completely assigned, and the effects of diastereotopism in cis-4-tert-butylcyclohexyl phenyl sulphoxide were rationalized. Substituent effects on the "0 chemical sbift of numerous sulphoxides and sulphones are discussed. An unusual paramagnetic y gauche effect on the "S nucleus was detected in cis-4-tert-butylcyclohexyl phenyl sulphone.

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“…Conventionally, C aryl -S bond formation requires high reaction temperatures and the use of toxic and high-boiling polar solvents. [4][5][6] A series of metal catalysts including Pd, 7 Cu, 8 Fe, 9 Co 10 and Ni 11 has been employed to promote this transformation under relatively mild conditions. However, the existing methods still suffer from some drawbacks.…”

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confidence: 99%

Microwave-Assisted, Metal- and Solvent-Free Synthesis of Diaryl Thioethers from Aryl Halides and Carbon Disulfide in the Presence of [DBUH]⁺[OAc]⁻

Zhou

2016

Journal of Chemical Research

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Aryl sulfides and their derivatives have found widespread applications in biological science, medicinal chemistry and materials chemistry. [1][2][3] Therefore, C-S bond formation is of great importance and has attracted much attention in recent years. Conventionally, C aryl -S bond formation requires high reaction temperatures and the use of toxic and high-boiling polar solvents. [4][5][6] A series of metal catalysts including Pd, 7 Cu, 8 Fe, 9 Co 10 and Ni 11 has been employed to promote this transformation under relatively mild conditions. However, the existing methods still suffer from some drawbacks. For example, the direct use of thiols is environmentally unfriendly due to their foul smell, volatility and toxicity. In addition, they are prone to undergo oxidative homocoupling to form disulfides. To address these issues, different thiol surrogates such as thiourea, 12 potassium thiocyanate, 13 potassium ethyl xanthogenate, 14 potassium thioacetate, 15 metal sulfides 16 and carbon disulfide 17 have been employed. Green solvents have also been successfully used for C aryl -S bond formation reactions. 12,18 These protocols, however, still require high reaction temperatures and long reaction times as well as the use of metal catalysts. Thus, the development of an efficient and environmentally benign process for C aryl -S bond formation is still in demand and remains a challenge.Recently, Zheng et al. reported a highly efficient way to capture CS 2 by employing an ionic liquid ([DBUH] + [OAc] -). 19 This kind of ionic liquid can not only activate CS 2 but also shows promising reusability as a solvent. Inspired by this work, we envisioned whether this ionic liquid could be applied to C aryl -S bond formation where CS 2 was used as a thiol surrogate. Here we report a microwave-assisted direct coupling between aryl halides and carbon disulfide in ionic liquid [DBUH] + [OAc] -(Scheme 1). Results and discussionInitially, 1-iodo-4-nitrobenzene (1a) was selected as the model substrate to optimise the reaction conditions (Table 1). The solvent exhibited a strong influence on this transformation. Aprotic organic solvents including toluene, acetonitrile, ethyl acetate and dichloromethane afforded moderate to good yields of the product 2a (Table 1, entries 2-5), whereas reaction in polar protic solvents, such as methanol, provided only 20% yield of product 2a (Table 1, entry 6). The reaction did not take place in the presence of water (Table 1, entry 7). Encouragingly, Microwave-assisted, metal-and solvent-free synthesis of diaryl thioethers from aryl halides and carbon disulfide in the presence of [DBUH] + [OAc] -

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Synthesis of Thioethers. Amide Solvent-Promoted Nucleophilic Displacement of Halide by Thiolate Ion

Cited by 97 publications

References 0 publications

A Highly Efficient Palladium‐Catalyzed One‐Pot Synthesis of Unsymmetrical Aryl Alkyl Thioethers under Mild Conditions in Water

A Highly Efficient Palladium‐Catalyzed One‐Pot Synthesis of Unsymmetrical Aryl Alkyl Thioethers under Mild Conditions in Water

¹H, ¹³C, ¹⁷O and ³³S NMR investigation of some cyclohexyl phenyl sulphides, sulphoxides and sulphones

Microwave-Assisted, Metal- and Solvent-Free Synthesis of Diaryl Thioethers from Aryl Halides and Carbon Disulfide in the Presence of [DBUH]⁺[OAc]⁻

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Synthesis of Thioethers. Amide Solvent-Promoted Nucleophilic Displacement of Halide by Thiolate Ion

Cited by 97 publications

References 0 publications

A Highly Efficient Palladium‐Catalyzed One‐Pot Synthesis of Unsymmetrical Aryl Alkyl Thioethers under Mild Conditions in Water

A Highly Efficient Palladium‐Catalyzed One‐Pot Synthesis of Unsymmetrical Aryl Alkyl Thioethers under Mild Conditions in Water

1H, 13C, 17O and 33S NMR investigation of some cyclohexyl phenyl sulphides, sulphoxides and sulphones

Microwave-Assisted, Metal- and Solvent-Free Synthesis of Diaryl Thioethers from Aryl Halides and Carbon Disulfide in the Presence of [DBUH]+[OAc]−

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¹H, ¹³C, ¹⁷O and ³³S NMR investigation of some cyclohexyl phenyl sulphides, sulphoxides and sulphones

Microwave-Assisted, Metal- and Solvent-Free Synthesis of Diaryl Thioethers from Aryl Halides and Carbon Disulfide in the Presence of [DBUH]⁺[OAc]⁻