Photolysis of 3-Aryl-3-(trifluoromethyl)diazirines: A Caveat Regarding Their Use in Photoaffinity Probes

Matthew Platz, Atnaf S. Admasu, Stefan Kwiatkowski, Peter J. Crocker, Nobuyuki Imai, David S. Watt

Research output: Contribution to journalArticlepeer-review

41 Scopus citations


The photolysis of 3-(4-tolyl)-3-(trifIuoromethyl)diazirine in the presence of benzene, methanol, carbon tetrachloride, cyclohexane, triethylsilane, or diethyl amine led to photo-products consistent with the intermediary of a singlet carbine. In the case of diethyl amine, the photo insertion into the N-H bond of diethyl amine produced the expected abduct, l-(diethylamino)-2,2,2-trifluoro-l-(4-tolyl)ethane. However, the base-catalyzed elimination of hydrogen fluoride from this abduct afforded an examine, a-(diethylamino)-ß,ß-difluoro-4-methylstyrene, and the subsequent hydrolysis of this examine furnished diethyl amine and 2,2-difluoro-l-(4-tolyl)ethanone. This elimination and hydrolysis sequence effectively reversed the photo-insertion process. A similar photo insertion and hydrolysis process using 3-(4-rc-octylphenyl)-3-(trifluoromethyl)diazirine also produced 2,2-difluoro-l-(4-π-octylphenyl)ethanone in modest yield. These results suggest that the photo insertion products from 3-aryl-3-(trifluoromethyl)-diazirines in biological systems may suffer similar fates limiting, in part, their utility in obtaining primary sequence data.

Original languageEnglish
Pages (from-to)337-341
Number of pages5
JournalBioconjugate Chemistry
Issue number5
StatePublished - Sep 1 1991

Bibliographical note

Funding Information:
We thank the National Institutes of Health (HD 25961) and the National Science Foundation (CHE-8814950) for theirgenerousfinancialsupport.

ASJC Scopus subject areas

  • Biotechnology
  • Bioengineering
  • Biomedical Engineering
  • Pharmacology
  • Pharmaceutical Science
  • Organic Chemistry


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