Synthesis of sulphenyl halides and sulphenamides

Drabowicz, J.; Kiełbasiński, P.; Mikołajczyk, M.

doi:10.1002/9780470772287.ch6

“…Taking advantage of the reversible elimination of a −SR group (33), we could next also develop a transfer bromothiolation of alkenes to prepare 1,2-bromothioether derivatives, which are valuable synthetic intermediates usually accessed through multistep synthesis involving highly reactive RSBr reagents (34,35). Several terminal alkenes were successfully converted to the targeted bromothioether product under otherwise identical conditions, taking 2-bromoethyl phenyl sulfide (5 equivalents) as the PhS−Br donor (Fig.…”

mentioning

confidence: 99%

Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations

Dong

¹

,

Roeckl

²

,

Waldvogel

³

et al. 2021

Science

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Vicinal dibromides and dichlorides are important commodity chemicals and indispensable synthetic intermediates in modern chemistry that are traditionally synthesized using hazardous elemental chlorine and bromine. Meanwhile, the environmental persistence of halogenated pollutants necessitates improved approaches to accelerate their remediation. Here, we introduce an electrochemically assisted shuttle (e-shuttle) paradigm for the facile and scalable interconversion of alkenes and vicinal dihalides, a class of reactions that can be used both to synthesize useful dihalogenated molecules from simple alkenes and to recycle waste material through retro-dihalogenation. The reaction is demonstrated using 1,2-dibromoethane, as well as 1,1,1,2-tetrachloroethane or 1,2-dichloroethane, to dibrominate or dichlorinate, respectively, a wide range of alkenes in a simple setup with inexpensive graphite electrodes. Conversely, the hexachlorinated persistent pollutant lindane could be fully dechlorinated to benzene in soil samples using simple alkene acceptors.

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“…3A). Using this procedure, a series of mono-substituted, di-substituted and tri-substituted alkenes participated smoothly in the 1,2-transfer dichlorination reaction, with free alcohol (29, 35, and 37), ester (30), imide (32), phosphonate (33), sulfone (34), internal alkyne (37), and Ts and Boc protected amine moieties (38 and 39) well tolerated. Various styrene-derived alkenes were converted to the corresponding 1,2-dichlorides in good to excellent yield (42-52), leaving the Br, Cl, CN, CF3, 11 CHO, and COOH functional groups untouched.…”

Section: Fig 1 │ Reaction Design and Challenges Of Transfer Difunctionalizationmentioning

confidence: 99%

Merging Shuttle Reactions and Paired Electrolysis: E-Shuttle Unlocks Reversible Halogenations

Dong¹,

Röckl²,

Waldvogel³

et al. 2020

Preprint

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<p>Polyhalogenated molecules have found widespread applications as flame retardants, pest-control agents, polymers and pharmaceuticals. They also serve as versatile synthetic intermediates in organic chemistry due to the inherent reactivity of carbon-halogen bonds. Despite these attractive features, the preparation of polyhalogenated molecules still mainly relies on the use of highly toxic and corrosive halogenating reagents, such as Cl<sub>2</sub> and Br<sub>2</sub>, which are hazardous compounds to transport, store, and handle. Moreover, the use of such highly reactive reagents inherently makes the development of the reverse reactions, <i>retro</i>-dihalogenations, highly challenging, despite their potential for the recycling of persistent halogenated pollutants. Here, we introduce an electrochemically-assisted shuttle<i> (e-shuttle)</i> paradigm for the facile and scalable interconversion of alkenes and vicinal dihalides, a class of reactions which can be used both to synthesize useful polyhalogenated molecules from simple alkenes and to recycle waste material through <i>retro</i>-dihalogenation. The power of this reaction is best highlighted by an example, in which different soils contaminated with a persistent environmental pollutant (Lindane), could be directly used as Cl<sub>2</sub>-donors for the transfer dichlorination of simple feedstock alkenes, merging a recycling process with a synthetically relevant dichlorination reaction. We further demonstrate that this paired electrolysis-enabled shuttle protocol, which uses a simple setup and inexpensive electrodes, is applicable to four different, synthetically useful transfer halogenation reactions, and can be readily scaled-up to a decagram scale. In a broader context, the symbiotic merging of shuttle reactions and electrochemistry introduced in this work opens new horizons for safer transfer functionalization reactions that will address important challenges across the molecular sciences.</p> <div><br><div> </div> </div>

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“…Taking advantage of the reversible elimination of a ─SR group 31 , we could next also develop a transfer bromothiolation of alkenes to make 1,2-bromothioether derivatives which are valuable 5 synthetic intermediates usually accessed through multistep synthesis involving toxic and highly reactive R─SBr reagents 32,33 . Several terminal alkenes were successfully converted to the targeted bromothio-ether product, under otherwise identical conditions, taking 2-bromoethyl phenyl sulfide (21, 5 equiv.)…”

mentioning

confidence: 99%

“…3A). Using this procedure, a series of mono-substituted, di-substituted and tri-substituted alkenes participated smoothly in the 1,2-transfer dichlorination reaction, with free alcohol (29, 35, and 37), ester (30), imide (32), phosphonate (33), sulfone (34), internal alkyne (37), and Ts and Boc protected amine moieties (38 and 39) well tolerated. Various styrene-derived alkenes were converted to the corresponding 1,2-dichlorides in good to excellent yield (42-52), leaving the Br, Cl, CN, CF3, 11 CHO, and COOH functional groups untouched.…”

mentioning

confidence: 99%

Merging Shuttle Reactions and Paired Electrolysis: E-Shuttle Unlocks Reversible Halogenations

Dong¹,

Röckl²,

Waldvogel³

et al. 2020

Preprint

View full text Add to dashboard Cite

<p>Polyhalogenated molecules have found widespread applications as flame retardants, pest-control agents, polymers and pharmaceuticals. They also serve as versatile synthetic intermediates in organic chemistry due to the inherent reactivity of carbon-halogen bonds. Despite these attractive features, the preparation of polyhalogenated molecules still mainly relies on the use of highly toxic and corrosive halogenating reagents, such as Cl<sub>2</sub> and Br<sub>2</sub>, which are hazardous compounds to transport, store, and handle. Moreover, the use of such highly reactive reagents inherently makes the development of the reverse reactions, <i>retro</i>-dihalogenations, highly challenging, despite their potential for the recycling of persistent halogenated pollutants. Here, we introduce an electrochemically-assisted shuttle<i> (e-shuttle)</i> paradigm for the facile and scalable interconversion of alkenes and vicinal dihalides, a class of reactions which can be used both to synthesize useful polyhalogenated molecules from simple alkenes and to recycle waste material through <i>retro</i>-dihalogenation. The power of this reaction is best highlighted by an example, in which different soils contaminated with a persistent environmental pollutant (Lindane), could be directly used as Cl<sub>2</sub>-donors for the transfer dichlorination of simple feedstock alkenes, merging a recycling process with a synthetically relevant dichlorination reaction. We further demonstrate that this paired electrolysis-enabled shuttle protocol, which uses a simple setup and inexpensive electrodes, is applicable to four different, synthetically useful transfer halogenation reactions, and can be readily scaled-up to a decagram scale. In a broader context, the symbiotic merging of shuttle reactions and electrochemistry introduced in this work opens new horizons for safer transfer functionalization reactions that will address important challenges across the molecular sciences.</p> <div><br><div> </div> </div>

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Synthesis of sulphenyl halides and sulphenamides

Cited by 4 publications

References 192 publications

Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations

Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations

Merging Shuttle Reactions and Paired Electrolysis: E-Shuttle Unlocks Reversible Halogenations

Merging Shuttle Reactions and Paired Electrolysis: E-Shuttle Unlocks Reversible Halogenations

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