Facile Synthesis of Tuneable Azophosphonium Salts

Habraken, Evi R. M.; Zee, Lars J. C. van der; Vrande, Koen N. A. van de; Jupp, Andrew R.; Nieger, Martin; Ehlers, Andreas W.; Slootweg, J. Chris

doi:10.1002/ejic.201801546

Cited by 6 publications

(3 citation statements)

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“…The endocyclic N2N3 bond, measured at 1.341(2) Å, is also rather long for a NN bond. It is indeed longer than the average length measured for azophosphoniums 9 (1.272 Å on average), nonmetalated phosphazides (1.277 Å on average), or phosphine azido cations 10 (1.277 Å on average) available in the CCDC database (Figure 1). Such a bond length is reminiscent of the N−N bond reported by Stephan's group in 2018 when deprotonating a cyclic (amino)(aryl)nitrenium cation α to the nitrogen (Figure 1) for which the N−N bond length is 1.3584( 14) Å.…”

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confidence: 68%

Reaction of Phosphines with 1-Azido-(2-halogenomethyl)benzene Giving Aminophosphonium-Substituted Indazoles

et al. 2020

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The reaction between a 1-azido-(2-halogenomethyl)benzene and a phosphine gives different products depending on the nature of the halogen, the phosphine itself and the solvent employed. While PPh3 (2 equiv.) reacts with the chloro reagent in toluene to give the expected iminophosphorane-phosphonium adduct, trialkylphosphines (PCy3 and PEt3) surprisingly furnish an aminophosphonium substituted by a zwitterionic indazole. The bicyclic product can also form from PPh3 using the bromo reagent in acetonitrile. A mechanism is proposed for this cyclization based on DFT calculations.

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confidence: 68%

Reaction of Phosphines with 1-Azido-(2-halogenomethyl)benzene Giving Aminophosphonium-Substituted Indazoles

et al. 2020

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“…422 As for the case of heteroatom nucleophiles, Slootweg and coworkers reported the facile synthesis of tunable aryl azophosphonium salts through the reaction of para-substituted aryl diazonium salts with tritert-butylphosphine, leading to a range of colored compounds (16 examples, 55−96% yields). 423 Additionally, the one-pot reaction from anilines through diazotization and treatment with a trialkyl phosphite was reported, affording phosphonohydrazines in moderate yields (6 examples, 27−84% yields). 424 These two reactions utilized phosphine compounds as the nucleophiles.…”

Section: Nucleophilic Additions With Aryl Diazonium Cationmentioning

confidence: 99%

Recent Development of Aryl Diazonium Chemistry for the Derivatization of Aromatic Compounds

et al. 2021

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Aryl diazonium salts are versatile building blocks in organic synthesis. In light of the ever-increasing importance of aryl diazonium salts spanning most disciplines of the chemical sciences, we review the recent development of aryl diazonium chemistry over the past seven years (2013−2020). Special emphasis is put on various new transformations involving the generation of radical intermediates via thermal, photochemical, and electrochemical means. Recent advances in the development of transition metal-catalyzed reactions using aryl diazonium salts are also reviewed. Together, these newly developed transformations significantly expand the synthetic chemist's repertoire of aromatic carbon−carbon and carbon−heteroatom bond forming methods using aryl diazonium precursors, providing powerful tools for the synthesis and modification of complex molecular scaffolds.

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“…The scope of azophosphonium salts was extended by our group by altering the aryl ring as well as the phosphine, demonstrating the readily tuneability of this synthetic protocol (Figure 3). 34 For the use of tri-tert-butylphosphine a wide range of stable adducts (16) can be synthesized in various shades of purple, pink and red ([(p-R-C 6 H 4 )N 2 (Pt-Bu…”

Section: Scheme 12 Top: Reaction Of Aryldiazonium Salt [(P-cl-c 6 H 4 )N 2 ][Bf 4 ]mentioning

confidence: 99%

Diazonium Salts as Nitrogen-Based Lewis Acids

Habraken¹,

Jupp²,

Slootweg

2019

Synlett

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Aryldiazonium salts are widely used in many organic transformations with displacement of N2 or through addition to the terminal nitrogen. Such aryldiazonium salts can be viewed as N-based Lewis acids that can react with Lewis bases to synthesize a wide variety of azo compounds. Additionally, diazonium salts are known to undergo single-electron transfer and release N2, forming an aryl radical, which results in different reactivity. Herein, we provide a concise overview of the reactivity of aryldiazonium salts undergoing classical donor-acceptor reactivity or single-electron transfer.

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Facile Synthesis of Tuneable Azophosphonium Salts

Abstract: Azophosphonium salts have a facile synthesis and can be readily tuned at the para position of the aryl group and at the phosphorus position with the use of bulky phosphines, leading to a range of coloured compounds. A relation between [a] Van '

Cited by 6 publications

References 31 publications

Reaction of Phosphines with 1-Azido-(2-halogenomethyl)benzene Giving Aminophosphonium-Substituted Indazoles

Reaction of Phosphines with 1-Azido-(2-halogenomethyl)benzene Giving Aminophosphonium-Substituted Indazoles

Recent Development of Aryl Diazonium Chemistry for the Derivatization of Aromatic Compounds

Diazonium Salts as Nitrogen-Based Lewis Acids

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