American Chemical Society
jo402041u_si_001.pdf (728.53 kB)

Electrospray Ionization (ESI) Fragmentations and Dimethyldioxirane Reactivities of Three Diverse Lactams Having Full, Half, and Zero Resonance Energies

Download (728.53 kB)
journal contribution
posted on 2014-01-17, 00:00 authored by Kathleen M. Morgan, David J. Ashline, Jessica P. Morgan, Arthur Greenberg
Three lactams having, respectively, ∼20, ∼10, and 0 kcal/mol of resonance energy have been subjected to electrospray ionization mass spectrometry (ESI/MS) as well as to attempted reaction with dimethyldioxirane (DMDO). The ESI/MS for all three lactams are consistent with fragmentation from the N-protonated, rather than the O-protonated tautomer. Each exhibits a unique fragmentation pathway. DFT calculations are employed to provide insights concerning these pathways. N-Ethyl-2-pyrrolidinone and 1-azabicyclo­[3.3.1]­nonan-2-one, the full- and half-resonance lactams, are unreactive with DMDO. The “Kirby lactam” (3,5,7-trimethyl-1-azaadamantan-2-one) has zero resonance energy and reacts rapidly with DMDO to generate a mixture of reaction products. The structure assigned to one of these is the 2,2-dihydroxy-N-oxide, thought to be stabilized by intramolecular hydrogen bonding and buttressing by the methyl substituents. A reasonable pathway to this derivative might involve formation of an extremely labile N-oxide, in a purely formal sense, an example of the hitherto-unknown amide N-oxides, followed by hydration with traces of moisture.