1999 年 57 巻 4 号 p. 280-290
Reaction of formaldehyde with ammonia gives several kinds of products, including 3 : 3, 5 : 4, 6 : 4, and 7 : 6 adducts. The reaction of aldehydes with polyfunctional compounds having amino and hydroxy groups has been reported in the literature to produce a variety of unsaturated and saturated heterocycles. Detailed stereochemical studies on such monocyclic products using NMR spectroscopy have revealed that they are controlled by anomeric effects, repulsion of lone-pairs, 1, 3-interactions, and gauche effects.
Recently preparations of novel polyazapolyheterocycles by reactions of mono- and dialdehydes with mono-, di-, tri-, and tetraamines, and diaminoalcohols have been reported. These reactions have resulted in interesting and unanticipated caged, bridged, and macrocyclic products whose stereochemistries have been examined by NMR spectroscopy. Some stereoisomers were found to be consistent with predictions by heats of formation using MOPAC and steric energies using MM calculations and have been subsequently confirmed by X-ray crystallography.