title: Silicon migration from oxygen to carbon and decarbonylation in methoxytriphenylsiloxycarbene.
abstract: [reaction: see text] Thermolysis of 2-methoxy-2-triphenylsiloxy-5,5-dimethyl-Delta(3)-1,3, 4-oxadiazoline affords methyl triphenylsilylformate and methyl triphenylsilyl ether via methoxytriphenylsiloxycarbene. Kinetics show that the carbene undergoes reversible 1,2-triphenylsilyl migration (Brook rearrangement) as well as irreversible decarbonylation. Computed transition states and activation energies (B3LYP/6-31+G) suggest that the migration of the silyl group from oxygen to carbon occurs through an "in plane" transition state with the carbene lone pair forming a new bond to silicon. Decarbonylation involves a four-membered ring, achieved by nucleophilic attack of the oxygen atom of the methoxy group at silicon.
authors.affiliation: Department of Chemistry, McMaster University, 1280 Main Street West, Hamilton, Ontario, Canada.
authors.forename: J P
authors.initials: JP
authors.lastname: Pezacki
authors.forename: P G
authors.initials: PG
authors.lastname: Loncke
authors.forename: J P
authors.initials: JP
authors.lastname: Ross
authors.forename: J
authors.initials: J
authors.lastname: Warkentin
authors.forename: T A
authors.initials: TA
authors.lastname: Gadosy