83025-99-4Relevant academic research and scientific papers
Structure of the modified heme in allylbenzene-inactivated chloroperoxidase determined by Q-band CW and pulsed ENDOR
Lee, Hong-In,Dexter, Annette F.,Fann, Yang-Cheng,Lakner, Frederick J.,Hager, Lowell P.,Hoffman, Brian M.
, p. 4059 - 4069 (1997)
During the epoxidation of allylbenzene, chloroperoxidase (CPO) is converted to an inactive green species in which the prosthetic heme has been modified by addition of the alkene plus an oxygen atom (Dexter, A. F.; Hager, L. P. J. Am. Chem. Soc. 1995, 117,
A mechanistic study of the chromium(II)-mediated transformations of trichloromethyl alkyls and carbinols: evidence for carbene, carbyne, and carbenoid intermediates
Bejot, Romain,Tisserand, Steve,Li, De Run,Falck,Mioskowski, Charles
, p. 3855 - 3858 (2008/02/02)
Using CrCl2 in THF at room temperature, trichloromethyl carbinols and trichloromethylalkanes are readily transformed to the highly reactive α-chlorocarbenes, carbynes and α-chloro-α-chromium(III) vinylidene carbenoids. A mechanistic study is carried out to determine the nature of the intermediates.
Mechanistic Features of Allylic Hydrogen Abstraction by Alkoxy Radicals
Kwart, H.,Brechbiel, M.,Miles, W.,Kwart, L.D.
, p. 4524 - 4528 (2007/10/02)
A TS(excit) of angular H abstraction from allylbenzene in the course of the allylic acetoxylation reaction was previously invoked to explain a temperature-independent primary KIE; kH/kD = 2.90.This reaction geometry is now fully supported by the finding of inverse α-secondary deuterium isotope effects at both ends of the double bond in allylbenzene; (kH/kD)αC1 = 0.977 and (kH/kD)αC2 = 0.985.In keeping with these results an unsymmetrically structured, bridged radical intermediate, formed by the interaction of t-BuO with the allylic double bond, steers the reaction course.Such a complex is recognized to be unusual since most of the verified cases of radical bridging involve heteroatom centers capable of octet expansion.A discussion is also given of the factors determining the relative influence of benzene and double bond participation in the H-abstraction reactions of allylbenzene, which possesses both of these activating functions.
