Quantum Chemical Analysis of Heteroarylnitrenium Ions and Mechanisms for Their Self-Destruction

Michael B. Sullivan and Christopher J. Cramer

J. Am. Chem. Soc., 122 (23), 5588-5596, 2000.

Contribution from the Department of Chemistry and Supercomputer Institute, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455-0431

Received February 15, 2000

Revised Manuscript Received April 17, 2000

ABSTRACT:

Singlet-triplet state-energy splittings in arylnitrenium ions are substantially reduced when the aromatic system is heterocyclic with nitrogen atoms incorporated at ring positions that would otherwise better stabilize the formally exocyclic positive charge through resonance. Ring contraction rearrangements of singlet arylnitrenium ions with a nitrogen atom at an ortho position are predicted to proceed with barrier heights that become lower with increasing substitution of nitrogen atoms at other positions. Predilection to delocalize positive charge also controls the relative facility with which (i) N-acetylarylnitrenium ions undergo ring closure to form 2-oxazolium cations and (ii) arylnitrenium ions are subject to nucleophilic aromatic substitution by water.

DOI: 10.1021/ja0005486