Synthesis of optically active hydroxyphosphonates

Guliaiko, Irina V.; Nesterov, V. I.; Sheiko, S. G.; Kolodiazhnyi, Oleg I.; Freytag, Mat­thias; Jones, Peter G.; Schmutzler, Reinhard

doi:10.1002/hc.20391

Cited by 23 publications

(7 citation statements)

References 21 publications

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“…97 Kolodiazhnyi et al also demonstrated that racemic α-hydroxyphosphonates bearing dimenthyl auxiliary, prepared in the reaction of aldehydes with (−)-56 catalysed by DBU, could be used to obtain the corresponding α-ketophosphonates 92a-c (by oxidation with the use of pyridinium dichromate/trimethylchlorosilane) that were subsequently reduced in diastereoselective fashion to optically pure α-hydroxyphosphonates 89a,c,f (Scheme 31). 98,99 Similar strategy was also applied to β-ketophosphonate 93. The latter was prepared in a three-step one-pot procedure from dimenthyl methylphosphonate by the reaction with butyllithium to form the corresponding carbanion that was further reacted with cuprous bromide to form cuprous derivative that was finally reacted with acyl chlorides to produce the appropriate β-ketophosphonates.…”

Section: Organic and Biomolecular Chemistry Reviewmentioning

confidence: 99%

Asymmetric synthesis of organophosphorus compounds using H–P reagents derived from chiral alcohols

Gbubele

Olszewski

2021

Org. Biomol. Chem.

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Section: Organic and Biomolecular Chemistry Reviewmentioning

confidence: 99%

Asymmetric synthesis of organophosphorus compounds using H–P reagents derived from chiral alcohols

Gbubele

Olszewski

2021

Org. Biomol. Chem.

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“…The reaction proceeded rather slowly, but with good yields of chiral hydroxyphosphonates. To complete the reaction, it took from 1 to 3 days at +20 • C. The structure of the products was studied by X-ray diffraction analysis [32]. The stereoselectivity of the reaction depended on the structure of the initial reagents and reaction conditions.…”

Section: Diastereoselective Substitution Reactionsmentioning

confidence: 99%

“…In particular, the chiral reducing agent NaBH 4 -Pro, derived from NaBH 4 and (S)-proline, reduced ketophosphonates with good enantioselectivity. This reducing agent has been applied to the synthesis of a number of hydroxyphosphonates (Figure 13) [32,33]. reducing agent has been applied to the synthesis of a number of hydroxyphosphonates (Figure 13) [32,33].…”

Section: Diastereoselective Substitution Reactionsmentioning

confidence: 99%

“…This reducing agent has been applied to the synthesis of a number of hydroxyphosphonates (Figure 13) [32,33]. reducing agent has been applied to the synthesis of a number of hydroxyphosphonates (Figure 13) [32,33]. An interesting method is the enantioselective reduction of ketophosphonates by complexes of borohydrides with tartaric acid [33][34][35][36][37].…”

Section: Diastereoselective Substitution Reactionsmentioning

confidence: 99%

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Stereoselective Syntheses of Organophosphorus Compounds

Kolodiazhnyi,

Kolodiazhna

2024

Symmetry

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The review is devoted to the theoretical and synthetic aspects of the stereochemistry of organophosphorus compounds. Organophosphorus compounds are not only widely exist in biologically active pharmaceuticals and agrochemicals, but also have widespread applications in material science and organic synthesis as ligands for transition metal complexes. One of the mainstreams for the development in this field is the creation of biologically active organophosphorus compounds that are searched and used as drugs or plant-protecting agents, which leads to the elaboration of advanced methods and monitoring, yielding up-to-date approaches to perform synthesis in an environmentally friendly manner. The review consists of two parts. The first part presents methods for the asymmetric synthesis of organophosphorus compounds using asymmetric organocatalysis and metal complex catalysis. In the review is described the nature of the chirality generation in the prebiotic period, the mechanisms of asymmetric induction, and double stereodifferentiation are discussed. The use of these methods for the preparation of chiral phosphorus analogs of natural compounds (phosphono-isonorstatin, phosphono-GABOB, phosphacarnitine, bis-phosphonates, and others) is described. Some data concerning of λ5-phosphanediones as metaphosphate anion analogues are also reported. The second part of the presented review shows examples of the use of these methods for the synthesis of phosphorus analogues of natural compounds—chiral phosphonoamino acids and hydroxyphosphonates: phosphonoaspartic acid, phosphonoglutamic acid, phosphonohomoproline, chiral bis-phosphonates. The reaction of dehydration aromatization with the formation of pho sphono isoindolinones, including isoindolinone bis-phosphonates, has been studied. Some of the synthesized compounds showed biological activity as protein tyrosine phosphatase inhibitors. A phosphonic analogue of iso-norstatine was synthesized. A stereoselective method for the synthesis of tetradecapentaenoic acid derivatives was developed.

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“…In other variations, pyridinium dichromate [ 105 ] or pyridinium chlorochromate [ 106 ] were applied successfully to give α-ketophosphonates 35 . The reaction under discussion was also reported using KMnO 4 as the oxidant ( Scheme 18 ).…”

Section: Reactions Of α-Hydroxyphosphonatesmentioning

confidence: 99%

Synthesis and Reactions of α-Hydroxyphosphonates

Rádai

Keglevich

2018

Molecules

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This review summarizes the main synthetic routes towards α-hydroxyphosphonates that are known as enzyme inhibitors, herbicides and antioxidants, moreover, a number of representatives express antibacterial or antifungal effect. Special attention is devoted to green chemical aspects. α-Hydroxyphosphonates are also versatile intermediates for other valuable derivatives. O-Alkylation and O-acylation are typical reactions to afford α-alkoxy-, or α-acyloxyphosphonates, respectively. The oxidation of hydroxyphosphonates leads to ketophosphonates. The hydroxy function at the α carbon atom of hydroxyphosphonates may be replaced by a halogen atom. α-Aminophosphonates formed in the nucleophilic substitution reaction of α-hydroxyphosphonates with primary or secondary amines are also potentially bioactive compounds. Another typical reaction is the base-catalyzed rearrangement of α-hydroxy-phosphonates to phosphates. Hydrolysis of the ester function of hydroxyphosphonates leads to the corresponding phosphonic acids.

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Synthesis of optically active hydroxyphosphonates

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Cited by 23 publications

References 21 publications

Asymmetric synthesis of organophosphorus compounds using H–P reagents derived from chiral alcohols

Asymmetric synthesis of organophosphorus compounds using H–P reagents derived from chiral alcohols

Stereoselective Syntheses of Organophosphorus Compounds

Synthesis and Reactions of α-Hydroxyphosphonates

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