An Azide-Functionalized Nitronyl Nitroxide Radical: Synthesis, Characterization and Staudinger-Bertozzi Ligation Reactivity

An azide-functionalized nitronyl nitroxide was successfully synthesized and its reactivity towards the Staudinger-Bertozzi ligation was explored. While a model reaction in solution showed the conversion of the nitronyl nitroxide to an imino nitroxide radical, the same reaction at the interface of gold nanoparticles allowed for successful covalent incorporation of the nitronyl nitroxide radical onto the nanoparticles

Organic reducing agents. Reduction of electron deficient bromides by 1,2,2,6,6-pentamethylpiperidine (PMP)/mercaptoethanol

1,2,2,6,6-pentamethylpiperidine (PMP) is shown to be an effective reducing agent for the radical chain conversion of primary bromoesters to the corresponding esters. The problem of inefficient reduction of tertiary bromoesters in these reactions has been overcome by the addition of an alkyl thiol which mediates the hydrogen atom transfer between the two hindered alkyl centers.NRC publication: Ye

Remote substituent effects on the reactivity of 9-aryl- and 9,10-diarylanthracene radical cations with anions and amines

Radical cations of 9-aryl- and 9,10-diarylanthracenes with substituents on the 4 position of the aryl rings (PA-X+ and DPA-X+, respectively) have been generated by photoionization in acetonitrile. Their reactivity with n-butylamine (n-BuNH2) and 1,4-diazabicyclo[2.2.2]octane (DABCO) and a number of anions (CH3CO2-, Br-, CN-, N3-) has been studied using nanosecond laser flash photolysis. Reactions proceed by electron transfer and/or nucleophilic addition. Using PA-X and DPA-X as chemical probes, simple criteria are established that allow one mechanistic pathway to be distinguished from another. When electron transfer is thermodynamically feasible, this pathway dominates (e.g., DABCO and azide). For endothermic electron transfer, addition is not necessarily the preferred ultimate reaction pathway and an inner sphere process (addition/homolysis) can compete. In these cases other, criteria including steric factors and the strength of the incipient bond become important. Simple kinetic criteria and an approach to estimate the thermochemistry of the addition process are developed. It is clear from these studies that reactivity trends in the radical cation chemistry cannot be generalized as easily as those in carbocation chemistry. This has some implications concerning the development and utility of "clock" reactions in radical cation chemistry.Peer reviewed: YesNRC publication: Ye