Reactivity of Primary Phosphines and Primary Phosphine Sulfides towards Imines

Jan-Willem Lamberink; Paul D Boyle; Joe B Gilroy; James J Noël; Johanna M Blacquiere; Paul J Ragogna

doi:10.1002/chem.202201565

Reactivity of Primary Phosphines and Primary Phosphine Sulfides towards Imines

Chemistry. 2022 Sep 16;28(52):e202201565. doi: 10.1002/chem.202201565. Epub 2022 Jul 26.

Authors

Jan-Willem Lamberink¹, Paul D Boyle¹, Joe B Gilroy¹, James J Noël^{1

2}, Johanna M Blacquiere¹, Paul J Ragogna¹

Affiliations

¹ Department of Chemistry, Centre for Advanced Materials and Biomaterials Research (CAMBR), The University of Western Ontario, N6A 587, London, Ontario, Canada.
² Surface Science Western, The University of Western Ontario, N6G 0J3, London, Ontario, Canada.

PMID: 35882523
DOI: 10.1002/chem.202201565

Abstract

Reactivity of primary phosphines with two stoichiometric equivalents of imine results in the formation of bis-α-aminophosphines (2 a-e), which can be subsequently oxidized in the presence of S₈ or H₂ O₂ to generate air stable bis-α-aminophosphine sulfides (2 b-m(S/O)). To elucidate the mechanism of this three-component reaction, Hammett analysis, kinetic isotope effect (KIE), and trapping experiments were performed. Ultimately a P(V)-P(III) tautomerization is invoked, followed by nucleophilic attack by the P(III) species to generate the desired products.

Keywords: imine; main group; mechanism; nucleophilicity; primary phosphine.

Abstract

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