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Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents**

Fabian Dankert, Jan‐Erik Siewert, Priyanka Gupta, Florian Weigend, Christian Hering‐Junghans

2022Angewandte Chemie International Edition41 citationsDOIOpen Access PDF

Abstract

Abstract N‐containing molecules are mostly derived from ammonia (NH 3 ). Ammonia activation has been demonstrated for single transition metal centers as well as for low‐valent main group species. Phosphinidenes, mono‐valent phosphorus species, can be stabilized by phosphines, giving so‐called phosphanylidenephosphoranes of the type RP(PR′ 3 ). We demonstrate the facile, metal‐free NH 3 activation using ArP(PMe 3 ), affording for the first time isolable secondary aminophosphines ArP(H)NH 2 . DFT studies reveal that two molecules of NH 3 act in concert to facilitate an NH 3 for PMe 3 exchange. Furthermore, H 2 NR and HNR 2 activation is demonstrated.

Topics & Concepts

Wittig reactionReagentMetalChemistryStereochemistryOrganic chemistryAsymmetric Hydrogenation and CatalysisOrganophosphorus compounds synthesisPhosphorus compounds and reactions
Metal‐Free N−H Bond Activation by Phospha‐Wittig Reagents** | Litcius