jp506154s_si_001.pdf (56.38 MB)
O‑Ylide and π‑Complex Formation in Reactions of a Carbene with Dibenzo and Monobenzo Crown Ethers
journal contribution
posted on 2014-08-14, 00:00 authored by Pablo
A. Hoijemberg, Robert A. Moss, David V. Feinblum, Karsten Krogh-JespersenReactions
of p-nitrophenylchlorocarbene (PNPCC)
with various dibenzo crown ethers produce O-ylides
and π-complexes; the reactions can be followed via the spectral
signatures of the carbene and the products. The O-ylides form most rapidly, but over time they decay in favor of the
more stable π-complexes. Extensive computational studies support
and refine appropriate structural and mechanistic conjectures. Reactions
of PNPCC with monobenzo crown ethers afford only the spectral signatures
of O-ylides; monobenzo π-complexes are either
not formed in significant concentrations or are spectroscopically
silent.