30287-20-8Relevant academic research and scientific papers
Intramolecular and intermolecular kinetic isotope effects (KIE) in the nitrosoarene ene reaction: Experimental evidence for reversible intermediate formation
Adam, Waldemar,Krebs, Oliver,Orfanopoulos, Michael,Stratakis, Manolis,Vougioukalakis, Georgios C.
, p. 2420 - 2425 (2003)
The intramolecular and intermolecular kinetic isotope effects (KIE) have been determined for the nitrosoarene ene reaction with deuterium-stereolabeled 2,3-dimethyl-2-butenes (TME). trans-TME-d6 (kH/kD = 3.0) and gem-TME-d6 (kH/kD = 4.0) show large intramolecular primary isotope effects. In contrast, the intramolecular competition in cis-TME-d6 (kH/kD = 1.5) and the intermolecular competition for the TME-d0/TME-d12 pair (kH/kD = 1.98) show considerably smaller, but mechanistically significant kinetic isotope effects. The latter fact is rationalized in terms of reversible formation of a three-membered-ring intermediate, namely the aziridine N-oxide, or a similar unsymmetrical, polarized diradical in the first step of the reaction. Such reversibility has also been implied earlier for triazolinedione (TAD) and singlet oxygen (1O2) with deuterium-stereolabeled 2-butenes, but of the three enophiles, ArNO is the most sensitive toward reversibility, which is due to its moderate reactivity and its high steric demand.
On the Reaction of the Nitroso Group with Olefins. Mechanisms of Ene Reactions
Seymour, Catherine A.,Greene, Frederick D.
, p. 5226 - 5227 (1982)
Intra- and intermolecular isotope effects point to a two-step process for the reaction of pentafluoronitrosobenzene with tetramethylethylene to afford the ene product, 4--rate-determining formation of an intermediate (for which the aziridine N-oxide 5 is suggested) followed by C-H (or C-D) cleavage to the ene product.
