title: Ozonolysis of bicyclic 1,2-dioxines: initial scope and mechanistic insights.
abstract: The ozonolysis of bicyclic 1,2-dioxines was investigated using a variety of 1,4-disubstituted 1,2-dioxines along with a 1,3-dialkyl and steroidal example, with yields ranging from moderate to excellent. Two different pathways were observed upon reaction of the 1,4-disubstituted 1,2-dioxines with ozone; one pathway saw the "expected" results, that is, cleavage of the olefinic moiety with generation of 1,4-dicarbonyl 1,2-dioxines, while the other pathway revealed a previously unobserved rearrangement involving cleavage of the peroxide linkage along with loss of either CO or CO(2). Several unsymmetrical ozonolyses were also performed to further investigate the origins of this rearrangement, and initial mechanistic insights into the fragmentation pathways are discussed.
authors.affiliation: School of Agriculture, Food and Wine, The University of Adelaide, South Australia 5005, Australia.
authors.forename: Nicole M
authors.initials: NM
authors.lastname: Cain
authors.forename: Edward R T
authors.initials: ER
authors.lastname: Tiekink
authors.forename: Dennis K
authors.initials: DK
authors.lastname: Taylor
mesh_terms: D001643:Bridged Bicyclo Compounds / Q000737:chemistry*; D004147:Dioxins / Q000737:chemistry*; D015394:Molecular Structure; D010126:Ozone / Q000737:chemistry*
chemical_list: D001643:Bridged Bicyclo Compounds; D004147:Dioxins; D010126:Ozone