Themechanism of the reaction of sulfonic acids with the electrophilictrifluoromethylating reagents 1-trifluoromethyl-1,2-benziodoxol-3-(1H)-one (1) and1-trifluoromethyl-1,3-dihydro-3,3-dimethyl-1,2-benziodoxole (2) has been carefully analyzed usingrate and competition studies.  Thereagents show related, but distinctly different behavior towards sulfonicacids.  Relative rates of reaction ofsulfonic acids toward 1 and 2 as well as several other related hypervalentiodine based electrophilic trifluoromethylating reagents have also beendetermined, showing 1 to be mostreactive toward sulfonic acids.  Inaddition, initial mechanistic investigations, on the basis of competitionstudies, have also been carried out on the reaction of 1 and 2 with thiolsshowing 2 to be significantly (approximately14 times) more reactive toward thiols. The results of these studies suggest completely different mechanisms ofaction of 1 and 2 toward hard (oxygen) and soft (sulfur) nucleophiles anddemonstrate the differences in reactivites of 1 and 2 toward differentsubstrates.

Insight
into the mechanism of electrophilic trifluoromethylation by CF<sub>3</sub>-bearing 1,2-benziodoxoles

239th National Meeting (2010)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.

Insight into the mechanism of electrophilic trifluoromethylation by CF3-bearing 1,2-benziodoxoles

Insight into the mechanism of electrophilic trifluoromethylation by CF₃-bearing 1,2-benziodoxoles