Mechanistic organic chemistry in a microreactor. Zeolite-controlled photooxidations of organic sulfides.
The intrazeolite and solution photooxygenations of a series of sulfides have been compared. The unusual zeolite environment enhances the rates of reaction, it suppresses the Pummerer rearrangements, and it has a dramatic effect on the sulfoxide/sulfone ratio. A detailed kinetic study utilizing trapping experiments and intramolecular competition provides evidence for cation complexation to a persulfoxide intermediate as the underlying phenomenon for the unique intrazeolite behavior. For example, the enhanced rate of reaction is traced to the cation stabilization of the persulfoxide toward unproductive decomposition to substrate and triplet oxygen.
Clennan
Edward L
EL
Department of Chemistry, University of Wyoming, Laramie, Wyoming 82071, USA. Clennane@uwyo.edu
Zhou
Wenhui
W
Chan
Jacqueline
J