79722-34-2Relevant articles and documents
Bromide Ion Promoted β-Elimination in α-Bromo Ester Substrates. Evidence for an Intermediate in the E2C Reaction
Kwart, Harold,Gaffney, Anne
, p. 4502 - 4508 (2007/10/02)
The TDKIE criteria of transition state geometry in H-transfer reactions have been applied in the title reactions; a bent transition state consistent with the geometry of the E2C reaction has been verified by the results of intramolecular and intermolecular competition modes of determining kH/kD as a function of temperature.The extraordinary magnitude measured for the α secondary deuterium isotope effect in the E2C mechanism is reconciled with a very loose transition state and an acute angle of H-abstraction in the course of rearward approach to Cα by the promoter base.The virtual identity of the inter- and intramolecular isotope effects can be correlated by the assumption of a reaction intermediate of trigonal-bipyramid structure surrounding Cα and in which the abstractable H and D atoms are equally available to the action of the promoter base.The properties of this intermediate (4), by way of contrast with the transition state of an SN2 process, are discussed in detail.