18666-64-3Relevant academic research and scientific papers
Silicon migration from oxygen to carbon and decarbonylation in methoxytriphenylsiloxycarbene
Pezacki, John Paul,Loncke, Paul G.,Ross, Joseph P.,Warkentin, John,Gadosy, Timothy A.
, p. 2733 - 2736 (2000)
Thermolysis of 2-methoxy-2-triphenylsiloxy-5,5-dimethyl-Δ3-1,3,4-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.
