Trapping of peroxidic intermediates with sulfur and phosphorus centered electrophiles

Abstract

The trapping ability of a new peroxidic trapping agent relative to several well‐established trapping agents was measured. Two different methods for this measurement were utilized. It was shown that adamantylidene adamantane reacts under the trapping conditions to give adamantylidene adamantane epoxide via a more complicated process than previously recognized and is consequently an inappropriate system to make this measurement. In contrast, the use of diethyl sulfide is straightforward and gives reliable values. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:51–56, 1998

Experimental and DFT Computational Insight into Nitrosamine Photochemistry—Oxygen Matters

“…Thus, O atom transfer of the peroxy intermediate to trapping agents trimethylphosphite, (MeO) 3 P, and triphenylphosphine, Ph 3 P, were investigated next. Phosphites have been reported as in situ trapping agents for heteroatom and hydrocarbon peroxides. − Thus, we hypothesized that O-transfer of the peroxy intermediate to (MeO) 3 P will occur in the photoreaction of 1 , as we observe. The photolysis of 1 with (MeO) 3 P and 18 O 2 led to 18 O-labeled phosphate [(MeO) 3 P 18 O], indicating that the oxygen atom transferred to phosphite originated from 18 O 2 .…”

Persulfoxide: Key Intermediate in Reactions of Singlet Oxygen with Sulfides

“…The ability of persulfoxides to transfer an oxygen atom to substrates Y (Path e Scheme ) has attracted attention because of the interest in monooxygenase enzyme models . The spectrum of Y substrates which have been examined includes electrophilic substrates such as sulfoxides, , sulfinate esters, sulfinamides, phosphites, and sulfenate esters . Nucleophilic substrates such as alkyl substituted alkenes, on the other hand, do not function as oxygen atom acceptors.…”

Photooxygenations of Sulfur Compounds

“…Sulfoxides are not the only molecules that can accept an oxygen from a persulfoxide. Electrophilic trapping agents such as phosphites [49], sulfenate esters [50], sulfinate esters [51], and sulfinamides [51] can also remove an oxygen from the PS. An interesting example of the nucleophilic reaction of a PS was observed during the photooxygenation of [1-(ethylthio)-1-methylethoxy]trimethylsilane, 11 [52] (Figure 32.6).…”