Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 135, Issue 19, Pages 7349-7354Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja402833w
Keywords
-
Categories
Funding
- EPSRC [EP/I003479/1]
- EaStCHEM
- EPSRC U.K. National Electron Paramagnetic Resonance Service at the University of Manchester
- EPSRC National Mass Spectrometry Service in Swansea
- Engineering and Physical Sciences Research Council [EP/I003479/1] Funding Source: researchfish
- EPSRC [EP/I003479/1] Funding Source: UKRI
Ask authors/readers for more resources
A set of oxime carbamates having N-alkyl and N,N-dialkyl substituents were prepared via carbonyldiimidazole intermediates. It was shown by EPR spectroscopy that they underwent clean homolysis of their N-O bonds upon UV photolysis. During photolysis of acetophenone O-allylcarbamoyl oxime, the corresponding oxazolidin-2-onylmethyl radical was detected by EPR spectroscopy, providing the first evidence that N-monosubstituted carbamoyloxyl radicals can hold their structural integrity. N,N-Disubstituted carbamoyloxyl radicals dissociated rapidly at the lowest accessible temperatures. Above room temperature, both types of oxime carbamate acted as selective new precursors for aminyl and iminyl radicals. Rate parameters were measured for 5-exo cyclization of N-benzyl-N-pent-4-enylaminyl radicals; the rate constant was smaller than for C-centered and O-centered analogues. Oxime carbamates derived from the volatile diethylamine afforded aryliminyl radicals that proved convenient for phenanthridine preparations.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available