Phospha-Mannich reactions of RPH2, R2PH, and R3P

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

doi:10.1080/10426507.2022.2036149

Cited by 9 publications

(5 citation statements)

References 729 publications

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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%

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%

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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“…One ligand family we sought to explore was 1,5-diaza-3,7-diphosphacyclooctanes, abbreviated as P 2 N 2 ligands. These are modular and readily accessible from the corresponding phosphine and amine via condensation with formaldehyde . However, their use in organic synthesis has been sparsely reported. , Herein we report an evaluation of diverse Mizoroki–Heck reactions, which reveals this ligand class provides both high reactivity and selectivity with a range of substrates, including surprising regiocontrol in the couplings of aryl triflates with styrenes (Scheme C).…”

Section: Introductionmentioning

confidence: 96%

Controlling Reactivity and Selectivity in the Mizoroki–Heck Reaction: High Throughput Evaluation of 1,5-Diaza-3,7-diphosphacyclooctane Ligands

Isbrandt,

Chapple,

et al. 2024

J. Am. Chem. Soc.

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We report a high throughput evaluation of the Mizoroki−Heck reaction of diverse olefin coupling partners. Comparison of different ligands revealed the 1,5-diaza-3,7-diphosphacyclooctane (P 2 N 2 ) scaffold to be more broadly applicable than common "gold standard" ligands, demonstrating that this family of readily accessible diphosphines has unrecognized potential in organic synthesis. In particular, two structurally related P 2 N 2 ligands were identified to enable the regiodivergent arylation of styrenes. By simply altering the phosphorus substituent from a phenyl to tert-butyl group, both the linear and branched Mizoroki− Heck products can be obtained in high regioisomeric ratios. Experimental and computational mechanistic studies were performed to further probe the origin of selectivity, which suggests that both ligands coordinate to the metal in a similar manner but that rigid positioning of the phosphorus substituent forces contact with the incoming olefin in a π−π interaction (for P-Ph ligands) or with steric clash (for P-t Bu ligands), dictating the regiocontrol.

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Phospha-Mannich reactions of RPH₂, R₂PH, and R₃P

Cited by 9 publications

References 729 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

Controlling Reactivity and Selectivity in the Mizoroki–Heck Reaction: High Throughput Evaluation of 1,5-Diaza-3,7-diphosphacyclooctane Ligands

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