Reactivity of Primary Phosphines and Primary Phosphine Sulfides towards Imines

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 H2O2 to generate air stable bis‐α‐aminophosphine sulfides (2 b–m(S/O)). To elucidate the mechanism of t...

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Bibliographic Details
Published in:Chemistry : a European journal 2022-09, Vol.28 (52), p.n/a
Main Authors: Lamberink, Jan‐Willem, Boyle, Paul D., Gilroy, Joe B., Noël, James J., Blacquiere, Johanna M., Ragogna, Paul J.
Format: Article
Language:English
Subjects:
Chemistry
Hydrogen peroxide
imine
Imines
Isotope effect
main group
mechanism
nucleophilicity
Phosphine
Phosphines
primary phosphine
Sulfides
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Summary: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 H2O2 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. To P(III) or not to P(III). A three‐component mixture containing primary phosphine, chalcogen, and an imine affords a bis‐α‐aminophosphine chalcogenide. Mechanistic studies show an interesting dichotomy between the relative reactivities of P(III) vs. P(V) species towards imines.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202201565