Hilton, Margaret J.; Cheng, Bin; Buckley, Benjamin R.; Xu, Liping; Wiest, Olaf; Sigman, Matthew S. published the artcile< Relative reactivity of alkenyl alcohols in the palladium-catalyzed redox-relay Heck reaction>, Safety of (S)-4-(tert-Butyl)-2-(5-(trifluoromethyl)pyridin-2-yl)-4,5-dihydrooxazole, the main research area is reactivity alkenyl alc palladium catalyzed relay Heck; Heck reaction; competition experiments; redox-relay; relative rates of alkenes.
The relative rates of alkenyl alcs. in the Pd-catalyzed redox-relay Heck reaction were measured to examine the effect of their steric and electronic properties on the rate-determining step. Competition experiments between an allylic alkenyl alc. and two substrates with differing chain lengths revealed that the allylic alc. reacts 3-4 times faster in either case. Competition between di- and trisubstituted alkenyl alcs. provided an interesting scenario, in which the disubstituted alkene was consumed first followed by reaction of the trisubstituted alkene. Consistent with this observation, the transition structures for the migratory insertion of the aryl group into the di- and trisubstituted alkenes were calculated with a lower barrier for the former. An internal competition between a substrate containing two alcs. with differing chain lengths demonstrated the catalyst’s preference for migrating toward the closest alc. Addnl., increasing the electron-d. in the arene boronic acid promotes a faster reaction, which correlates with Hammett σp values to give a ρ of -0.87.
Tetrahedron published new progress about Alkenyl alcohols Role: PEP (Physical, Engineering or Chemical Process), PRP (Properties), RCT (Reactant), SPN (Synthetic Preparation), PROC (Process), RACT (Reactant or Reagent), PREP (Preparation). 1416819-91-4 belongs to class pyridine-derivatives, and the molecular formula is C13H15F3N2O, Safety of (S)-4-(tert-Butyl)-2-(5-(trifluoromethyl)pyridin-2-yl)-4,5-dihydrooxazole.