On the potential intermediacy of PhIBr₂ as a brominating agent

Abstract

PhIBr2, first purported to exist over 100 years ago, has been subject of few reports due to its low stability. However, a recent publication proposes a reaction of PIFA (PhI(OC(O)-CF3)2)...

ArI(NTf2)2: the boundary of oxidative capacity for ArIL2?

“…While we were undertaking this study Periana and co-workers isolated and spectroscopically characterized C 6 F 5 –I(NTf 2 ) 2 and showed that at elevated temperatures and pressures direct C–H activation of simple alkanes is possible. 13 They did not however confirm the structure by X-ray crystallography and in light of the previous misidentifications of PhI(OTf) 2 , as well as other recent cases involving structural misassignment of I( iii ) complexes, 14–16 it is important that structural confirmation of ArI(NTf 2 ) 2 is obtained. In this report we structurally characterize NO 2 –C 6 H 4 –I(NTf 2 ) 2 and provide analysis that shows these NTf 2 ligated species are significantly stronger oxidizing agents than NO 2 –C 6 H 4 –I(OTf) 2 , representing the current frontier in the oxidative ability of ArIL 2 and possibly the limit for this class of compound.…”

Alkene versus Aryl Chlorination in Asymmetric Hypervalent Iodine Catalysis: A Case Study

“…However, the literature does not present reports of utilizing 9 as reagents or catalysts in enantioselective bromo functionalizations. 23 However, recent studies by Wilson and Dutton showed that PhIBr 2 is an elusive compound, 24 making the application of linear bromo iodanes not feasible here. Therefore, we wondered if we could use the corresponding, more stable chloro iodanes instead to synthesize 4 in optically pure form.…”

Electrophilic activation of molecular bromine mediated by I(iii)

“…When anisole is reacted with molecular bromine, the reaction only takes 10 minutes at room temperature, demonstrating how unreactive this I–Br compound is in comparison to Br 2 itself. 7…”

“…8 However, we found that conditions that claimed to give PhIBr 2 are in fact generating in situ molecular bromine, which acts as the brominating agent. 7…”