Synthesis of 3-iodothiophenes via iodocyclization of (Z)-thiobutenynes

Santana, Amanda S.; Carvalho, Diego B.; Cassemiro, Nadla Soares; Viana, Luíz Henrique; Hurtado, Gabriela R.; Amaral, Marcos Serrou do; Kassab, Nájla Mohamad; Guerrero, Palimécio G.; Barbosa, Sandro L.; Dabdoub, Miguel J.; Baroni, Adriano C. M.

doi:10.1016/j.tetlet.2013.10.118

Cited by 27 publications

(19 citation statements)

References 32 publications

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“…Once again chloro- and bromocyclized products were obtained by our method in higher yields compared to the methodology reported by others 23b,24 indicating the superiority of our reaction conditions.…”

supporting

confidence: 62%

“… a Reaction Condition A: All reactions were performed using 0.30 mmol of the alkyne, 5 equiv of NaX, and 5 equiv of CuSO 4 •5H 2 O in 5 mL of EtOH at room temperature for 24 h. b Isolated yields. c Literature yield via halocyclization. d reference 23b. e reference 24. f reference 26 …”

Section: Figurementioning

confidence: 99%

“…This method requires mild reaction conditions resulting in very high yields of the products as compared with earlier reports. 23b,24 …”

mentioning

confidence: 99%

“…Our greener and milder reaction conditions resulted in the higher yields of chloro-, bromo-, and iodocyclized products compared to an earlier reported methodology. 23b,24 Replacing the phenyl group with a 3-thienyl moiety in the starting vinyl methyl thiol resulted in the cyclized chlorothiophene product 16 with an excellent yield of 91% (Table 1, entry 4). Our efforts to synthesize bromothiophene 17 failed, as cyclization of enyne 6 with NaBr and Cu 2 SO 4 •5H 2 O resulted in a complex reaction mixture.…”

mentioning

confidence: 99%

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Green synthesis of halogenated thiophenes, selenophenes and benzo[b]selenophenes using sodium halides as a source of electrophilic halogens

Kesharwani

Giraudy

Morgan

et al. 2017

Tetrahedron Letters

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Herein, we report the first synthesis of chlorinated benzo[b]selenophenes via environmentally friendly electrophilic chlorocyclization reaction using “table salt” as a source of “electrophilic chlorine” and ethanol as a solvent. In addition, the synthesis of diverse halogenated heterocycles, including 3-chloro, 3-bromo and 3-iodo thiophenes, selenophenes, and benzo[b]selenophenes was successfully accomplished under the same environmentally benign reaction conditions. This methodology has several advantages over other previously reported reactions as it employs simple starting compounds, an environmentally friendly solvent, ethanol, and non-toxic inorganic reagents under mild reaction conditions, resulting in the high product yields.

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supporting

confidence: 62%

Section: Figurementioning

confidence: 99%

“…This method requires mild reaction conditions resulting in very high yields of the products as compared with earlier reports. 23b,24 …”

mentioning

confidence: 99%

mentioning

confidence: 99%

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Green synthesis of halogenated thiophenes, selenophenes and benzo[b]selenophenes using sodium halides as a source of electrophilic halogens

Kesharwani

Giraudy

Morgan

et al. 2017

Tetrahedron Letters

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“…Interestingly, the ( Z )‐ and ( E )‐isomers of 3 obtained in these cases are easily separated by chromatographic column except for the ( Z )‐ and ( E )‐isomer of 3 k , which are inseparable. Both ( Z )‐ and ( E )‐vinyl sulfides are applied in the synthesis of functionalized materials and thiophene derivatives . It is noteworthy that the methods for the synthesis of ( E )‐vinyl sulfides are less reported…”

Section: Resultsmentioning

confidence: 99%

Application of DMSO in the Synthesis of 1,4-Disubstituted (But-1-en-3-ynyl)methylthioethers

et al. 2017

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Mapping the Interactions of I₂, I^., I⁻, and I⁺ with Alkynes and Their Roles in Iodocyclizations

Volpe

Aurelio

Gillin

et al. 2015

Chemistry A European J

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A combination of experiment and theory has been used to explore the mechanisms by which molecular iodine (I2 ) and iodonium ions (I(+) ) activate alkynes towards iodocyclization. Also included in the analysis are the roles of atomic iodine (I(.) ) and iodide ion (I(-) ) in mediating the competing addition of I2 to the alkyne. These studies show that I2 forms a bridged I2 -alkyne complex, in which both alkyne carbons are activated towards nucleophilic attack, even for quite polarized alkynes. By contrast, I(+) gives unsymmetrical, open iodovinyl cations, in which only one carbon is activated toward nucleophilic attack, especially for polarized alkynes. Addition of I2 to alkynes competes with iodocyclization, but is reversible. This fact, together with the capacity of I2 to activate both alkyne carbons towards nucleophilic attack, makes I2 the reagent of choice (superior to iodonium reagents) for iodocyclizations of resistant substrates. The differences in the nature of the activated intermediate formed with I2 versus I(+) can also be exploited to accomplish reagent-controlled 5-exo/6-endo-divergent iodocyclizations.

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Synthesis of 3-iodothiophenes via iodocyclization of (Z)-thiobutenynes

Cited by 27 publications

References 32 publications

Green synthesis of halogenated thiophenes, selenophenes and benzo[b]selenophenes using sodium halides as a source of electrophilic halogens

Green synthesis of halogenated thiophenes, selenophenes and benzo[b]selenophenes using sodium halides as a source of electrophilic halogens

Application of DMSO in the Synthesis of 1,4-Disubstituted (But-1-en-3-ynyl)methylthioethers

Mapping the Interactions of I₂, I^., I⁻, and I⁺ with Alkynes and Their Roles in Iodocyclizations

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Synthesis of 3-iodothiophenes via iodocyclization of (Z)-thiobutenynes

Cited by 27 publications

References 32 publications

Green synthesis of halogenated thiophenes, selenophenes and benzo[b]selenophenes using sodium halides as a source of electrophilic halogens

Green synthesis of halogenated thiophenes, selenophenes and benzo[b]selenophenes using sodium halides as a source of electrophilic halogens

Application of DMSO in the Synthesis of 1,4-Disubstituted (But-1-en-3-ynyl)methylthioethers

Mapping the Interactions of I2, I., I−, and I+ with Alkynes and Their Roles in Iodocyclizations

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Mapping the Interactions of I₂, I^., I⁻, and I⁺ with Alkynes and Their Roles in Iodocyclizations