Photodebromination of Bromothiophenes

Jeffries, Alfred T.; Párkányi, Cyril

doi:10.1515/znb-1976-0314

Cited by 9 publications

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References 11 publications

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“…2-Fluorothiophene ( 1a ) was not experimentally studied because the calculated barrier to cleave the Th–F bond was too high (42 kcal mol –1 ). 2-Bromo- and 2-iodothiophene ( 1c , d ) are known to undergo reductive dehalogenation upon irradiation , whereas the photochemistry of 2-chlorothiophene ( 1b ) is so far unexplored. Whether a diagnostic heteroaryl cation intermediate was formed was investigated by irradiation in the presence of allyltrimethylsilane (ATMS, 4 ) .…”

Section: Resultsmentioning

confidence: 99%

On the Route to the Photogeneration of Heteroaryl Cations. The Case of Halothiophenes

et al. 2016

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2-Chloro-, 2-bromo-, and 2-iodothiophenes undergo photochemical dehalogenation via the triplet state. In the presence of suitable π-bond nucleophiles, thienylation occurs with modest yield from chloro and bromo derivatives (via photogenerated triplet 2-thienyl cation). Specific trapping by using oxygen along with computational analysis carried out by means of a density functional method support that, in the case of iodo derivatives, homolytic thienyl-I bond fragmentation occurs first and heteroaryl cations are formed by electron transfer within the triplet radical pair, thus opening an indirect access to such cations.

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Section: Resultsmentioning

confidence: 99%