Stereochemical Studies with Aminophosphines and Related Compounds Having the 7-Phosphanorbornene Structure

摘要

Amines react with phosphinous chlorides having the anti-7-phosphanorbornene structure to give a mixture of syn. anti-aminophosphines. Structure assignment is straightforward from stereospecific effects and NMR spectra. Oxides and sulfides were prepared from the aminophosphines and characterized spectrally. Oxygen nucleophiles differ considerably in their reaction with such phosphinous chlorides and give only the product of retention. The different behavior of the amines is attributed to the lower apicophilicity of nitrogen in trigonal-bipyramidal intermediates that develop from an initially formed phosphoranide ion.