✦ LIBER ✦
Secondary α-deuterium kinetic isotope effects for addition of phenyl radical to benzyl isocyanides: An evidence of concerted mechanism.
✍ Scribed by Soo Kim Sung; Seung Lee Ki; Bong Hwang Soo; Jin Kim Hee
- Publisher
- Elsevier Science
- Year
- 1990
- Tongue
- French
- Weight
- 282 KB
- Volume
- 31
- Category
- Article
- ISSN
- 0040-4039
No coin nor oath required. For personal study only.
✦ Synopsis
Sumnary: Addition of phenyl radical to benzyl isocyanides gives benzonitrile and benzyl radicals, exhibiting positive Hamnett p=O.26 and notable secondary a-deuterium kinetic isotope effects.
These can be rationalized by concerted bond formation/cleavage occurring with polar transition states(TS).
Homolytic additions to alkyl isocyanides' have been well investigated and the epr studies3 confirm imidoyl radicals as the bona fide intermediates.
The intervention should thus unequivocally pronounce stepwise bond making , a, and breaking, b, for the reactions 2,3 as in eq 1.