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

Article abstract of DOI:10.1021/jo00383a003

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 in their 31P and 13C NMR spectra.Spectra for an isomer pair enriched in 15N also showed a structurally dependent ¹J_PN value.Oxides and sulfides were prepared from the aminophosphines and characterized spectrally.The 17O NMR spectra for a syn,anti pair were profoundly different and were useful for structural analysis.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.