Jc. Matasyoh et al., SYNTHESIS AND SPIN-TRAPPING STEREOCHEMISTRY OF THE CHIRAL SPIN TRAP, 5,5-DIMETHYL-3-PHENYLPYRROLINE-1-OXIDE, Magnetic resonance in chemistry, 34(5), 1996, pp. 351-359
A chiral spin trap, 5,5-dimethyl-3-phenylpyrroline-1-oxide (5), and se
veral hydroxylamines were synthesized, The structures and conformation
s of these compounds were investigated mainly by H-1 NMR spectroscopy.
This spin trap was used to trap carbon- and oxygen-centered radicals,
The corresponding hydrogen spin adduct was prepared by oxidizing the
hydroxylamine to the nitroxide radical. By the combination of H-1 NMR
and EPR results, it was shown that the conformation with the phenyl gr
oup of C-3 at the equatorial position is exclusively populated and its
lifetime is long compared with the EPR time-scale, Addition of carbon
-centered radicals to 5 leads to trans adducts whereas oxygen-centered
radicals formed cis isomers, These could be confirmed by the investig
ation of the monovalent oxidation products of the hydroxylamines. The
preference for these conformers is explained by the competition betwee
n steric and stereoelectronic effects, Despite the racemic nature of 5
and the formation of a new chiral center(s) in the spin adducts, the
presence of different diastereomers would not be observed by EPR where
as H-1 NMR studies of some of the nitrones showed clear evidence of di
astereomeric mixtures, However, the spin adduct of sec-hydroxybutyl ra
dical showed some linewidth effects,which could be attributed to the p
resence of two groups of diastereomers that were resolved by ENDOR spe
ctroscopy, In general, the spin adducts of 5 are closely related to th
ose of the well known DMPO, but the presence of a phenyl substituent a
t the 3-position results in a variation of the beta-H coupling constan
ts, In contrast to DMPO, 5 can scavenge short-lived radicals in aqueou
s and non-aqueous solutions.