Synthesis of Monosubstituted Phosphinic Acids:  Palladium-Catalyzed Cross-Coupling Reactions of Anilinium Hypophosphite

and, Jean-Luc Montchamp; Dumond, Yves

doi:10.1021/ja005721c

Cited by 114 publications

(64 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Precursors 283 were prepared by esterification of corresponding phosphinic acid, using a procedure described by Afarinkia (Scheme 56) [201]. When H-phosphinic acids were not commercially available, they were obtained by pallado-catalyzed arylation of anilinium hypophosphite [202]. The condensation gave a mixture of two diastereomers (syn/anti).…”

Section: Phosphinolactones As Anti-depressantsmentioning

confidence: 99%

Synthesis and Biological Applications of Phosphinates and Derivatives

Virieux

Volle

Bakalara

et al. 2014

Topics in Current Chemistry

View full text Add to dashboard Cite

This review first outlines general considerations on phosphinic acids and derivatives as bioisosteric groups. The next sections present key aspects of phosphinic acid-based molecules and include a brief description of the biological pathways involved for their activities. The synthetic aspects and the biological activities of such compounds reported in the literature between 2008 and 2013 are also described.

show abstract

Section: Phosphinolactones As Anti-depressantsmentioning

confidence: 99%

Synthesis and Biological Applications of Phosphinates and Derivatives

Virieux

Volle

Bakalara

et al. 2014

Topics in Current Chemistry

View full text Add to dashboard Cite

show abstract

“…31 Ethyl (4-methylphenyl)phenylphosphinate (8 h): [58] Oil, yield 79 % (411 mg). 31 Phenylphosphinic acid (8 k): [59] Oil, yield 74 % (210 mg). 31 …”

Section: -Nitrophenyl Phenyl Ether (5 J)mentioning

confidence: 99%

A Versatile and Efficient Ligand for Copper‐Catalyzed Formation of CN, CO, and PC Bonds: Pyrrolidine‐2‐Phosphonic Acid Phenyl Monoester

Rao

Jin

et al. 2006

Chemistry A European J

358

View full text Add to dashboard Cite

A new and readily available bidentate ligand, namely, pyrrolidine-2-phosphonic acid phenyl monoester (PPAPM), has been developed for the copper-catalyzed formation of C-N, C-O, and P-C bonds, and various N-, O-, and P-arylation products were synthesized in good to excellent yields by using the CuI/PPAPM catalyst system. Addition of the PPAPM ligand greatly increases the reactivity of the copper catalyst, and the resulting versatile and efficient catalyst system is of widespread and practical application in cross-coupling reactions.

show abstract

“…In this reaction, the added aminopropyltriethoxysilane serves as a base in the Pd-catalysed reaction, and enables the esterification of the phosphinic acid in situ. [17][18][19] …”

Section: Figurementioning

confidence: 99%

Synthesis of meta and para-substituted aromatic sulfonate derivatives of polydentate phenylazaphosphinate ligands: enhancement of the water solubility of emissive europium(iii) EuroTracker® dyes

2014

View full text Add to dashboard Cite

Publisher's copyright statement:Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Results and DiscussionThe target complexes ( Fig. 1) include three strongly absorbing and equivalent chromophores, in which there is meta or para-sulfonic acid substituent in the phenyl ring of the phosphinate moiety. The sulfonation of this position was not expected to perturb the chromophore characteristics significantly, as the phosphorus oxygen bond and the aryl groups to which it is attached are not strongly conjugated, unlike a trigonal amide or carboxylate substituent.Previous X-ray analysis studies of these phenylphosphinate lanthanide complexes have revealed that the phenyl rings are oriented in the same direction, away from the plane of the 9-N 3 ring, and with the same relative configuration at phosphorus. 13,15,16 These structural studies also confirmed that the phosphorus-oxygen double bond lies out of the plane of the aryl rings. A simple retrosynthetic analysis suggests the intermediacy of a 2,4,6-trisubstituted pyridine, with a 4-Br group, allowing a Sonogashira coupling reaction to an arylalkyne in a final ligand assembly step. the P centres respectively, as deduced by X-ray and CD studies on related systems. [13][14][15][16] OBC 2014 Delbianco 3In order to form the C-P bond, a palladium-catalysed reaction was envisaged, allowing insertion of a 2-pyridyl group into the P-H bond of a phenylphosphinic ester, bearing a suitably protected sulfonate group. Following the studies of Miller, 6a the behaviour of the trifluoroethyl and phenylsulfonate esters as protecting groups for the sulfonic acid moiety was examined; each ester was derived from 3 or 4-bromo-phenylsulfonyl chloride (Scheme 1).Palladium-catalysed coupling between the aryl bromide and anilinium hypophosphite proceeded in 70% yield for the trifluoroethyl ester, but failed with the phenyl ester, probably due to competitive insertion into the O-Ph bond. In this reaction, the added aminopropyltriethoxysilane serves as a base in the Pd-catalysed reaction, and enables the esterification of the phosphinic acid in situ. 17-19 Scheme 1The di-esters 3 and 4 were used in coupling reactions with 2-bromo-4-nitro-6-methyl pyridine in degassed toluene using Cl 2 Pd[bis(diphenylphosphino)ferrocene] as the catalyst to give the phosphinate esters 5 and 6 (Scheme 2). Bromination with neat acetyl bromide followed by reesterification of the phosphinic acid group with HC(OEt) 3 allowed the isolation of intermediates 7 and 8 in 77 and 81 % yield respectively. Treatme...

show abstract

Synthesis of Monosubstituted Phosphinic Acids: Palladium-Catalyzed Cross-Coupling Reactions of Anilinium Hypophosphite

Cited by 114 publications

References 11 publications

Synthesis and Biological Applications of Phosphinates and Derivatives

Synthesis and Biological Applications of Phosphinates and Derivatives

A Versatile and Efficient Ligand for Copper‐Catalyzed Formation of CN, CO, and PC Bonds: Pyrrolidine‐2‐Phosphonic Acid Phenyl Monoester

Synthesis of meta and para-substituted aromatic sulfonate derivatives of polydentate phenylazaphosphinate ligands: enhancement of the water solubility of emissive europium(iii) EuroTracker® dyes

Contact Info

Product

Resources

About