Phospha-Mannich reactions of PH<sub>3</sub>and its analogs

Moiseev, D. V.; James, Brian R.

doi:10.1080/10426507.2022.2036150

Cited by 8 publications

(6 citation statements)

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“…α-Aminophosphines are generally prepared by a variation of the “phospha-Mannich” reaction ,, by the interaction of diarylphosphine, aldehyde, and arylamine. We applied this approach to synthesize new α-aminophosphine 1 (Scheme ).…”

Section: Results and Discussionmentioning

confidence: 99%

“…Hexane was layered from a gas phase on the clear yellow solution. After 1 week, a mixture of yellow (6) and colorless (pyridinium chloride) crystals was formed, which were identified by SCXRD. Pyridinium chloride was identified by unit cell parameters (P − 1): a = 4.72 Å, b = 7.49 Å, c = 8.14 Å, α = 87.3°, β = 88.3°, γ = 87.5°, V = 287 Å 3 The mixture was stirred for 1 day at ambient temperature.…”

Section: Methodsmentioning

confidence: 99%

“…These transformations are often unexpected and can be overlooked . Reported examples are commonly represented by PPh 3 to PPh 2 – transformation with the coordination of the latter to a metal (e.g., Ru, Rh, Ir, and Pd). , P–C cleavage in α-aminophosphines including retro-phospha-Mannich reactions is less studied; generally, the skeletal structure of α-aminophosphines remains intact upon complex formation . Scarce metal-assisted reactions involve the P–C to P–H bond transformation.…”

Section: Introductionmentioning

confidence: 99%

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Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine

Afonin,

Martynenko,

Kolybalov

et al. 2023

Inorg. Chem.

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There is unceasing interest toward transformations of phosphine derivatives, which are facilitated by transition metals. We report a facile Pd(II)-and Pt(II)-assisted P−C bond cleavage in a luminescent 2-phenylbenzothiazole-based αmethylaminophosphine (PCN, 1). Specifically, reactions between 1 and [M(COD)Cl 2 ] (M = Pd, Pt; COD = cycloocta-1,5-diene) in different solvents (methylene chloride, acetonitrile, pyridine, toluene) resulted in the formation of PPh 2 − , captured either as a bridging ligand in binuclear complexes with a {M 2 (PPh 2 ) 2 } moiety or as an adduct to COD in [Pt 2 (PPh 2 COD) 2 Cl 2 ]. The heterocyclic part transforms to annulated c-CN + species with a 1,2-dihydroquinazoline cycle formed. In the presence of pyridine as a base, annulated form c-CN + destabilizes and undergoes reverse cyclization transforming to deprotonated CN form. Quantum-chemical density functional theory (DFT) calculations predict that a crucial step in the reactions involves proton transfer from the N atom of the amino group of PCN to a neighboring molecule. A combination of high photophysical sensitivity of c-CN + toward its immediate environment and rich structural capabilities in assembling (c-CN) 2 2+ pairs in different crystal packings in a family of phases with the general formula (c-CN) 2 [M 2 (PPh 2 ) 2 Cl 4 ] allows one to fine-tune the luminescence properties of the latter. The results were rationalized as a variation of π−π intercationic spacings, which tunes the degree of excitedstate charge transfer between c-CN + cations. As a result, compounds with relatively short interplanar π−π-separation between the cations show a stronger charge-transfer-mediated bathochromic shift.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine

Afonin,

Martynenko,

Kolybalov

et al. 2023

Inorg. Chem.

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“…These ligands were Unlike general synthetic phosphorus methodologies widely used for constructing P-C bonds [5], the transformations shown in Scheme 1 are simple condensations and employ, typically, secondary chlorophosphines or secondary phosphines as key starting reagents. In many instances, especially the Phospha-Mannich based reactions [6,7], work-up and isolations are straightforward and target P(III) compounds can often be accessed in good to high yields. Furthermore, in an industrial context, these reactions are important in the industrial preparation of flame retardants for cotton based materials using [P(CH 2 OH) 4 ] + salts and condensation with urea [8].…”

Section: Synthesis Of Selected Examplesmentioning

confidence: 99%

The Backbone of Success of P,N-Hybrid Ligands: Some Recent Developments

Smith

2022

Molecules

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Organophosphorus ligands are an invaluable family of compounds that continue to underpin important roles in disciplines such as coordination chemistry and catalysis. Their success can routinely be traced back to facile tuneability thus enabling a high degree of control over, for example, electronic and steric properties. Diphosphines, phosphorus compounds bearing two separated PIII donor atoms, are also highly valued and impart their own unique features, for example excellent chelating properties upon metal complexation. In many classical ligands of this type, the backbone connectivity has been based on all carbon spacers only but there is growing interest in embedding other donor atoms such as additional nitrogen (–NH–, –NR–) sites. This review will collate some important examples of ligands in this field, illustrate their role as ligands in coordination chemistry and highlight some of their reactivities and applications. It will be shown that incorporation of a nitrogen-based group can impart unusual reactivities and important catalytic applications.

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“…The synthesis of tris(aminomethyl)phosphines from tris(hydroxymethyl)phosphine and dialkylamines ( Figure 1 ) was first described by Coates and Hoye in 1960 [ 18 ]. Since then, the chemistry of this class of compounds has been developed systematically, resulting in a large number of tris(aminomethyl)phosphines synthesized and characterized [ 19 , 20 ].…”

Section: Introductionmentioning

confidence: 99%

Tris(aminomethyl)phosphines and Their Copper(I) (Pseudo)halide Complexes with Aromatic Diimines—A Critical Retrospection

Starosta

2023

Pharmaceuticals

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Metal complexes feature a wide range of available geometries, diversified lability, controllable hydrolytic stability, and easily available rich redox activity. These characteristics, combined with the specific properties of coordinated organic molecules, result in many different mechanisms of biological action, making each of the myriads of the classes of metal coordination compounds unique. This focused review presents combined and systematized results of the studies of a group of copper(I) (pseudo)halide complexes with aromatic diimines and tris(aminomethyl)phosphines of a general formula [CuX(NN)PR3], where X = I− or NCS−, NN = 2,2′-bipyridyl, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline or 2,2′-biquinoline, and PR3 = air-stable tris(aminomethyl)phosphines. The structural and electronic properties of the phosphine ligands and luminescent complexes are discussed. The complexes with 2,9-dimethyl-1,10-phenanthroline, apart from being air- and water-stable, exhibit a very high in vitro antimicrobial activity against the Staphylococcus aureus and Candida albicans. Moreover, some of these complexes also show a strong in vitro antitumor activity against human ovarian carcinoma cell lines: MDAH 2774 and SCOV 3, CT26 (mouse colon carcinoma), and A549 (human lung adenocarcinoma) cell lines. The tested complexes are moderately able to induce DNA lesions through free radical processes, however the trends do not reflect observed differences in biological activity.

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Phospha-Mannich reactions of PH₃and its analogs

Cited by 8 publications

References 543 publications

Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine

Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine

The Backbone of Success of P,N-Hybrid Ligands: Some Recent Developments

Tris(aminomethyl)phosphines and Their Copper(I) (Pseudo)halide Complexes with Aromatic Diimines—A Critical Retrospection

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Phospha-Mannich reactions of PH3and its analogs

Cited by 8 publications

References 543 publications

Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine

Pd(II)- and Pt(II)-Assisted P–C Activation/Cyclization Reactions with a Luminescent α-Aminophosphine

The Backbone of Success of P,N-Hybrid Ligands: Some Recent Developments

Tris(aminomethyl)phosphines and Their Copper(I) (Pseudo)halide Complexes with Aromatic Diimines—A Critical Retrospection

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Product

Resources

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Phospha-Mannich reactions of PH₃and its analogs