Hu, HY; Faraldos, JA; Coates, RM
A series of seven cyclopent-3-en-1-ylmethylamines bearing one, two, or three methyl substituents at the C2, C3, C4, or C-alpha positions, including the unsubstituted parent, was accessed by ring-closing metatheses of alpha,alpha-diallylacetonitrile (or methallyl variants) and alpha,alpha-diallylacetone followed by hydride reductions or reductive amination, or by Curtius degradations of alpha,alpha-dimethyl- and 2,2,3-trimethylcyclopent-3-enylacetic acids. Oxidation of the primary amines with Pb(OAc)(4) in CH2Cl2, CHCl3 or benzene in the presence of K2CO3 effected efficient intramolecular aziridinations, in all cases except the alpha-methyl analogue (16), to form the corresponding 1-azatricyclo[2.2.1.0(2,6)]heptanes, including the novel monoterpene analogues, 1-azatricyclene and the 2-azatricyclene enantiomers. The cumulative rate increases of aziridination reactions observed by H-1 NMR spectroscopy in CDCl3 resulting from the presence of one or two methyl groups on the cyclopentene double bond, in comparison to the rate of the unsubstituted parent amine (1:17.5:>280), indicate a highly electrophilic intermediate as the nitrene donor and a symmetrical aziridine-like transition state. A mechanism is outlined in which the amine displaces an acetate ligand from Pb(OAc)(4) to form a lead(IV) amide intermediate RNHPb(OAc)(3) proposed as the actual aziridinating species.