Oxygen-18 tracer use in ozonolysis mechanism studies. Results using the triphenylphosphine reduction method

Synthesis, microwave spectrum, electric dipole moment, molecular structure, and anomeric effect in fluoroethylene ozonide

“…This is the first definitive aldehyde-180 insertion test performed for a fluoroozonide although there have been several examples for alkyl and aryl alkenes. [47][48][49][50] In summary, the isotopic enrichments obtained during the ozonolysis of C2H3F and m-C2H2F2 indicate that the mechanism of ozonide formation is similar to that of the alkyl alkenes and consistent with Scheme I.…”

Ozonolysis of Bicyclic 1,2-Dioxines: Initial Scope and Mechanistic Insights

“…The ozonolysis of alkenes, first reported in 1840, remains one of the most important and classical methods for oxidative cleavage of alkenes . Since the basic mechanism was formulated by Criegee in the mid-1950s, , a large amount of work has been done on the mechanism, although not all details are fully understood. − While the Criegee mechanism has become generally accepted, a number of exceptions to this mechanism have appeared, prompting numerous “modified-Criegee” mechanisms to be reported. − Decomposition of the ozonides that result from this reaction can be carried out using a variety of different reagents, to furnish a number of functional products, with triphenylphosphine (PPh 3 ) being a widespread reagent for their reduction resulting in the formation of dicarbonyl products. , Despite all this attention, little precedent exists for the ozonolysis of bicyclic or other polycyclic alkenes, − and to the best of our knowledge, only two examples can be found within the literature involving the ozonolysis of alkene systems incorporating the 1,2-dioxine functionality. The natural product (−)-Warburganal ( 3 ) was synthesized in 15 steps from levopimaric acid in an overall yield of 2.7% .…”

“…26−28 Decomposition of the ozonides that result from this reaction can be carried out using a variety of different reagents, to furnish a number of functional products, with triphenylphosphine (PPh 3 ) being a widespread reagent for their reduction resulting in the formation of dicarbonyl products. 29,30 Despite all this attention, little precedent exists for the ozonolysis of bicyclic or other polycyclic alkenes, 31−33 and to the best of our knowledge, only two examples can be found within the literature involving the ozonolysis of alkene systems incorporating the 1,2-dioxine functionality. The natural product (−)-Warburganal (3) was synthesized in 15 steps from levopimaric acid in an overall yield of 2.7%.…”

Reaction of Diphenyldiazomethane with Singlet Oxygen Studied by Time-Resolved IR Spectroscopy

“…There are several routes for the synthesis of carbonyl oxides 1 : (i) the cycloreversion of 1,2,3-trioxolanes during the ozonolysis of alkenes (Criegee reaction); – (ii) the reaction of triplet carbenes 3 with molecular (triplet) oxygen, the triplet route; , and (iii) the reaction of diazo compounds 4 with singlet oxygen, the singlet route. − While there has been a lot of indirect evidence collected that carbonyl oxides 1 are indeed intermediates in the Criegee reaction, so far it was not possible to detect 1 as an intermediate in these reactions by direct spectroscopic methods. If 1 is indeed formed (which is generally accepted), it is too short-lived to be directly detected under these conditions.…”