Electronic effect on the kinetics of the diaza-cope rearrangement.
Hammett plot reveals that there is a significant electronic effect on the rate of resonance assisted hydrogen bond (RAHB) directed diaza-Cope rearrangement reaction with a rho value of 1.6. DFT computation shows that the rearrangement reaction becomes thermodynamically more favorable for the substrates with electron withdrawing substituents. A substrate with the nitro substituent (1a) reacts about 50-fold faster than that with the methoxy substituent (1g).
Lee
Dong-Nam
DN
Department of Chemistry, College of Natural Sciences, Kyonggi University, Suwon 443-760, Korea.
Kim
Hyunwoo
H
Mui
Leo
L
Myung
Seung-Woon
SW
Chin
Jik
J
Kim
Hae-Jo
HJ