J Org Chem. 2004 Oct 29;69(22):7486-94. doi: 10.1021/jo0486589.

Theoretical analysis of Lewis basicity based on local electron-donating ability. Origin of basic strength of cyclic amines.

The Journal of organic chemistry

Tomohiko Ohwada, Hajime Hirao, Atsushi Ogawa

PMID: 15497973 DOI: 10.1021/jo0486589

Abstract

It has been experimentally established that the proton affinities (PA), as well as the solution basicities (pK(BH)(+)), of aziridine derivatives are much smaller than those of the corresponding pyrrolidines and piperidines, though the basic strength of azetidines is close to those of pyrrolidines and piperidines. A simple idea of dependence of the basic strength on bond angles seems to be invalid. Because the basicity of cyclic amines is a fundamental property in organic chemistry, we revisited this topic in order to clarify quantitatively the intrinsic origin of the strength of Lewis basicity of the relevant amines, in particular, based on the local electron-donating ability of the amine nitrogen atoms evaluated in terms of the localized reactive hybrid orbital (RHO) concept. In the cases of representative N-substituents such as hydrogen, methyl, and phenyl groups, the electron-donating energy level of the nitrogen center, obtained by maximizing a kind of superdelocalizability, was shown to be correlated with the magnitudes of experimental and calculated gas-phase proton affinities. The present results strongly support the view that the C-N-C bond angle, i.e., angle strain, in the cyclic amines is not the major source of the difference in strength of basicity of these amines, but rather, the degree of pyramidalization around the nitrogen atom has a significant impact on the electron-donating ability of the nitrogen lone-pair orbital.

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