Reaction of benzolactams with triethyl phosphite prompted by phosphoryl chloride affords benzoannulated monophosphonates instead of expected bisphoshonates

Chmielewska, Ewa; Miszczyk, Patrycja; Kozłowska, Joanna; Prokopowicz, Monika; Młynarz, Piotr; Kafarski, Paweł

doi:10.1016/j.jorganchem.2015.03.005

Cited by 7 publications

(4 citation statements)

References 36 publications

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“…The formation of a Vilsmayer-Haack-like intermediate is also proposed in this case with the further addition of a nucleophilic phosphorus reagent. This assumption is additionally supported by studies on the use of structurally variable imine salts as substrates for synthesis of compounds 11 (Scheme 6) [41][42][43][44][45].…”

Section: Synthesis From Amidesmentioning

confidence: 85%

“…On the other hand, this reaction is not suitable for the conversion of benzoannulated lactams, and mixtures of the desired bisphosphonates and monophosphonates of variable structures were obtained (compounds 6, 7, 8 and 9, Scheme 5). In fact, monophosphonates are usually major products, and the reaction course is dependent on the size of the substrate aliphatic ring [44]. Additionally, these bisphosphonates and monophosphonates appeared to be unstable upon acid hydrolysis and upon storage, and undergo degradation with cleavage of the carbon-to-phosphorus bond (for example compound 10, Scheme 5 Scheme 6.…”

Section: Synthesis From Amidesmentioning

confidence: 99%

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Synthetic Procedures Leading towards Aminobisphosphonates

Chmielewska

Kafarski

2016

Molecules

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Abstract:Growing interest in the biological activity of aminobisphosphonates has stimulated the development of methods for their synthesis. Although several general procedures were previously elaborated to reach this goal, aminobisphosphonate chemistry is still developing quite substantially. Thus, innovative modifications of the existing commonly used reactions, as well as development of new procedures, are presented in this review, concentrating on recent achievements. Additionally, selected examples of aminobisphosphonate derivatization illustrate their usefulness for obtaining new diagnostic and therapeutic agents.

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Section: Synthesis From Amidesmentioning

confidence: 85%

Section: Synthesis From Amidesmentioning

confidence: 99%

Synthetic Procedures Leading towards Aminobisphosphonates

Chmielewska

Kafarski

2016

Molecules

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“…A reaction of pyrrolidin-2-one with phosphites in the presence of phosphoryl chloride leading to pyrrolidine-2,2bis(phosphonates) should also be mentioned here. An illustrative example 39 together with the proposed mechanism is given in Scheme 6. The reaction proceeds via the initial formation of a Vilsmayer-Haack-like intermediate I, and includes two subsequent Arbuzov-type rearrangements.…”

Section: Short Review Syn Thesismentioning

confidence: 99%

Synthesis of Phosphaproline Derivatives: A Short Overview

et al. 2019

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Pyrrolidine-based phosphonates, analogues of the natural amino acid proline, possess a diverse set of biological activity. The goal of this short review is to summarize the major developments in the synthesis of phosphaproline derivatives reported since 2004 with special emphasis on the mechanisms and limitations of the methods presented.1 Introduction2 Phosphorylation of Pyrrolidine Derivatives2.1 Syntheses via Pudovik Reaction2.2 Syntheses via Arbuzov Reaction2.3 Decarboxylative Phosphorylation of Proline2.4 Direct C–H Bond Phosphorylation2.5 Other Reactions2.6 Overview of Phosphorylation Methods3 Synthesis of 2-Phosphorylpyrrolidines from Acyclic Precursors3.1 Cyclization of 4-Substituted Butylamine Derivatives3.2 [3+2]-Dipolar Cycloaddition of α-Iminophosphonates3.3 Cyclization of Aminoalkynes and 4-Aminocarbonyl Compounds4 Conclusions

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“…Finally, the formation of lithium derivatives or Grignard reagents using aryl halides as substrates may be also employed [ 2 , 6 , 7 ]. In the past decade, interesting methods of nontypical specific procedures for the synthesis of heteroaromatic phosphonates have been studied and elaborated [ 12 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 ].…”

Section: Introductionmentioning

confidence: 99%

One-Pot Phosphonylation of Heteroaromatic Lithium Reagents: The Scope and Limitations of Its Use for the Synthesis of Heteroaromatic Phosphonates

et al. 2023

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A one-pot lithiation–phosphonylation procedure was elaborated as a method to prepare heteroaromatic phosphonic acids. It relied on the direct lithiation of heteroaromatics followed by phosphonylation with diethyl chlorophosphite and then oxidation with hydrogen peroxide. This protocol provided the desired phosphonates with satisfactory yields. This procedure also had some limitations in its dependence on the accessibility and stability of the lithiated heterocyclic compounds. The same procedure could be applied to phosphonylation of aromatic compounds, which do not undergo direct lithiation and thus require the use of their bromides as substrates. The obtained compounds showed weak antiproliferative activity when tested on three cancer cell lines.

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Reaction of benzolactams with triethyl phosphite prompted by phosphoryl chloride affords benzoannulated monophosphonates instead of expected bisphoshonates

Cited by 7 publications

References 36 publications

Synthetic Procedures Leading towards Aminobisphosphonates

Synthetic Procedures Leading towards Aminobisphosphonates

Synthesis of Phosphaproline Derivatives: A Short Overview

One-Pot Phosphonylation of Heteroaromatic Lithium Reagents: The Scope and Limitations of Its Use for the Synthesis of Heteroaromatic Phosphonates

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