Phosphorylating Power of Red Phosphorus towards Aldehydes in Basic and in Acidic Media

The phosphonic acid functional group, which is characterized by a phosphorus atom bonded to three oxygen atoms (two hydroxy groups and one P=O double bond) and one carbon atom, is employed for many applications due to its structural analogy with the phosphate moiety or to its coordination or supramolecular properties. Phosphonic acids were used for their bioactive properties (drug, pro-drug), for bone targeting, for the design of supramolecular or hybrid materials, for the functionalization of surfaces, for analytical purposes, for medical imaging or as phosphoantigen. These applications are covering a large panel of research fields including chemistry, biology and physics thus making the synthesis of phosphonic acids a determinant question for numerous research projects. This review gives, first, an overview of the different fields of application of phosphonic acids that are illustrated with studies mainly selected over the last 20 years. Further, this review reports the different methods that can be used for the synthesis of phosphonic acids from dialkyl or diaryl phosphonate, from dichlorophosphine or dichlorophosphine oxide, from phosphonodiamide, or by oxidation of phosphinic acid. Direct methods that make use of phosphorous acid (H3PO3) and that produce a phosphonic acid functional group simultaneously to the formation of the P–C bond, are also surveyed. Among all these methods, the dealkylation of dialkyl phosphonates under either acidic conditions (HCl) or using the McKenna procedure (a two-step reaction that makes use of bromotrimethylsilane followed by methanolysis) constitute the best methods to prepare phosphonic acids.

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“…38 ). However, the benzylphosphonic acid ( 136 ) was formed simultaneously with phosphoric acid thus requiring a purification step [ 253 ].…”

Section: Reviewmentioning

confidence: 99%

Phosphonic acid: preparation and applications

Sevrain¹,

Berchel²,

Couthon³

et al. 2017

Beilstein J. Org. Chem.

149

103

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“…To initiate our investigations, we examined the reaction of ethyl benzoyl(diethoxymethyl)phosphinate (1 a) and acetone with l-proline as the catalyst. The effects of catalyst loading ( [12][13][14][15]. With 20 mol % l-proline and HCOOH at 0-5 8C (Table 1, entry 14) or 10 mol % l-proline and ACOH at 0-5 8C ( Table 1, entry 15), good yields and high ee values were achieved for both of the two diastereomers.…”

Section: Resultsmentioning

confidence: 99%

“…As far as we know, only one reaction has been reported for such a process: the transformation of phosphinic acid to phosphonic acid in the presence of hydriodic acid. [12] Nevertheless, most of the reactions were performed under strongly acidic conditions with elevated temperature.…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

A Synthetic Study of Chiral α‐Hydroxy‐H‐Phosphinates Based on Proline Catalysis

Yao

Yuan

2013

Chemistry A European J

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A highly enantioselective synthesis of α-hydroxyphosphinates was achieved based on the L-proline-catalyzed aldol reaction of α-acylphosphinates and acetone. Due to the preexisting chirality at the phosphorus center, mixtures of two diastereomers of the α-hydroxyphosphinates were obtained in moderate to good yields, with simultaneously high enantioselectivity for both diastereomers. The products could be converted into α-hydroxy-H-phosphinates with satisfactory yields. Furthermore, an unprecedented oxidation-reduction reaction of the α-hydroxyphosphinates or α-hydroxy-H-phosphinates to form phosphonates was observed, and the mechanism involved in such a chemical transformation is discussed.

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“…On the basis of literature reports for the activation of phosphinic acids [17][18][19] and the reactions reported for diimines, 20 we believe that the present process proceeds via the activation of α-hydroxy-H-phosphinic acid by TMSCl and attack of activated intermediate 21,22 4 to the protonated diimine giving an α-imino-α′-hydroxyphosphinic acid intermediate 5 which undergoes subsequent hydrolysis in the workup to the α-amino-α′-hydroxyphosphinic acid compound (Scheme 4).…”

Section: Methodsmentioning

confidence: 91%

Novel Method for the Synthesis of α-Amino-α′-hydroxyalkylphosphinic Acids and Bis(α-aminoalkyl)phosphinic Acids: Nuclephilic Addition of α-Hydroxy-H-phosphinic Acids to Diimines

Kaboudin

Haghighat

Alaie

et al. 2012

Synlett

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We report here a novel and simple method for the synthesis of α-amino-α′-hydroxyalkylphosphinic acids in good yields in two simple steps without any protection-deprotection steps. We have developed an efficient method for the synthesis of α-amino-α′-hydroxyalkylphosphinic acids via the reaction of easily available α-hydroxyalkylphosphinic acids with diimines. Treatment of α-hydroxyalkylphosphinic acids with diimines in the presence of trimethylsilyl chloride (TMSCl) gives α-amino-α′-hydroxyalkylphosphinic acids in good yields. The reaction gave a mixture of two diastereomeric forms of α-amino-α′-hydroxyalkylphosphinic acids. The difference in solubility in organic solvents allowed us to readily separate the diastereoisomers.Phosphorus-carbon bond formation is an active and important research area for the preparation of organophosphorus compounds such as phosphinates. 1 Phosphinic peptides and pseudopepides are an important class of compounds that exhibit a variety of interesting and useful properties in biological activities. 2 The structure of the phosphinic functional group mimics the transition state of peptide hydrolysis, and the symmetric nature of phosphinic acid derivatives is expected to benefit in their binding to the homodimer of HIV-protease having C 2 -axis symmetry. 3 α-Functionalized phosphinic acid derivatives have attracted a great deal of attention due to their usefulness both in medicinal and material chemistry. 4 Among the α-functional phosphinic acids, α-hydroxyphosphinic acids, and α-aminophosphinic are interesting classes of compounds possessing broad biological activities. 5 Some α-hydroxyphosphinic acids are useful intermediates for preparing α-hydroxyphosphinyl peptides showing good inhibitory activity against renin. 6 α-Aminoalkylphosphinic derivatives have potential biological properties such as antibacterial, herbicidal, and fungicidal activity. 7 Furthermore, the conjunction of two functionalities in the same molecule such as α-amino-α′-hydroxyphosphinates or α,α′-diaminophophinates affords powerful inhibitors of HIV-1 protease and human aminopeptidase N (CD13). 8 In contrast to the widely studied synthesis of 1-amino or 1-hydroxy phosphinic acid derivatives, relatively few papers have reported on the chemistry of α-amino-α′-hydroxyphosphinates or α,α′-diaminophophinates. 9 There is currently only one available method, described by Drag and Oleksyzyn in 2005, 10 for the synthesis of α-amino-α′-hydroxyphosphinates starting from α-aminoalkylphosphinic acids. However, this method involves a severalstep process, requiring drastic reaction conditions, anaerobic and anhydrous conditions for some steps, long reaction times, several protection-deprotection steps, and gives low overall yields and side products. Diimines are good precursors for the synthesis of numerous organic compounds, especially heterocyclic compounds. 11 These readily accessible precursors can be produced by the reaction of aromatic aldehydes with aqueous ammonia. 12 Recently, we have reported the reaction of diimines with...

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Phosphorylating Power of Red Phosphorus towards Aldehydes in Basic and in Acidic Media

Cited by 23 publications

References 45 publications

Phosphonic acid: preparation and applications

Phosphonic acid: preparation and applications

A Synthetic Study of Chiral α‐Hydroxy‐H‐Phosphinates Based on Proline Catalysis

Novel Method for the Synthesis of α-Amino-α′-hydroxyalkylphosphinic Acids and Bis(α-aminoalkyl)phosphinic Acids: Nuclephilic Addition of α-Hydroxy-H-phosphinic Acids to Diimines

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