Stereoselective synthesis of fluorinated aminoglycosyl phosphonates

Bouwman, Sanne; Orru, Romano V. A.; Ruijter, Eelco

doi:10.1039/c4ob02317j

Cited by 18 publications

(15 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Overall, LiCF 2 P(O)(OEt) 2 was generated from LDA (4.2 equiv) and HCF 2 P(O)(OEt) 2 (4.3 equiv) in THF at −60 °C. 16 The much less stable Grignard analogue was in turn prepared by bromine−magnesium exchange, reacting diethyl bromodifluoro-methylphosphonate (BrCF 2 P(O)(OEt) 2 ) with i-PrMgCl (1.2 M in Et 2 O) and LiBr in THF at −75 °C. 17 Due to significant decomposition of the magnesium reagent during the course of the reaction, a large excess was mandatory (i.e., 8 equiv).…”

mentioning

confidence: 99%

Tunable Approach for the Stereoselective Synthesis of 1-C-Diethylphosphono(difluoromethyl) Iminosugars as Glycosyl Phosphate Mimics

et al. 2017

View full text Add to dashboard Cite

show abstract

mentioning

confidence: 99%

Tunable Approach for the Stereoselective Synthesis of 1-C-Diethylphosphono(difluoromethyl) Iminosugars as Glycosyl Phosphate Mimics

et al. 2017

View full text Add to dashboard Cite

show abstract

“…Despite several attempts, alkylation with some methylating agents (MeI/AgNO 3 , MeOTf, Meerwein's salt) or halogenation with N ‐halogenosuccinimides were unsuccessful. 2‐Nitroglycals have been recognized as very useful glycosyl donors for Michael additions, Diels‐Alder reactions, or [3+2] cycloadditions . However, nitration of thioglycal 3 , under various experimental conditions, did not work.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of 2‐Substituted Thioglycals from Carbohydrate‐Derived Ketene Dithioacetals

et al. 2020

View full text Add to dashboard Cite

A novel strategy for the synthesis of 2-substituted thioglycals has been developed from a carbohydrate-derived ketene dithioacetal in a two-step sequence. The introduction of various electrophilic groups at the double bond of the ketene dithioacetal was achieved before the elimination of the thioalkyl group to yield 2-substituted thioglycals. Removal of the [a] G. Merieux, M. Buchotte, M. Muzard, R. Plantier-Royon the corresponding exo-glycals in the furanose series. Recently, trifluoromethylated six-membered thioglycals were prepared via a multi-step synthetic sequence with a regioselective [4+2]cycloaddition between a fluorinated dithiocarboxylate and 1acetoxybutadiene in the first step. [18] As carbohydrate-derived sulfonium compounds are known to be an interesting class of glycosidase inhibitors, [19] we were also interested in the alkylation at the sulfur atom of the C-2 substituted thioglycals leading to 6-membered ring unsaturated sulfonium compounds. Scheme 7. Synthesis of 2-substituted thioglycals 15 and 16. Scheme 8. Preparation of sulfonium compound 18 and 18′ from thioglycal 16.

show abstract

“…Importantly, by introducing rigidity in the carbohydrate framework as featured in product 83 af , it was possible to achieve the preferential formation of the biologically important α‐anomer and get insights into the reaction mechanism. The synthetic utility of the products was demonstrated [136] …”

Section: Synthetic Methodsmentioning

confidence: 99%

Recent Advances in Synthesis of Difluoromethylene Phosphonates for Biological Applications

et al. 2021

View full text Add to dashboard Cite

For almost 40 years, difluoromethylene phosphonates have proven to be versatile molecular tools in biochemical studies owing to their close resemblance to naturally occurring phosphates and phosphonates. As bioisosteric, non‐hydrolyzable analogs of these essential molecules, difluoromethylene phosphonates can target the critical parts of the cellular machinery and therefore exhibit a diverse spectrum of biological activity. In the past ten years, there have appeared many new methods for the synthesis of difluoromethylene phosphonates. Most notably, photoredox catalysis has firmly entered the field, while cross‐coupling and nucleophilic strategies have met considerable elaboration and refinement, entirely in accord with the current trends in synthetic organic chemistry. Herein, we introduce difluoromethylene phosphonates as a distinct, high‐tech subclass of synthetic phosphonates resulting from the research efforts on the cross‐section of organophosphorus, organofluorine, and bioorganic chemistry. We then proceed to the discussion of general methods for the preparation of difluoromethylene phosphonates, comprehensively reviewing reactions developed in the past 15 years while providing the context of earlier works where appropriate. Finally, we present selected examples of molecules with high biological activity, their biological targets, and the synthetic steps employed for their preparation.

show abstract

Stereoselective synthesis of fluorinated aminoglycosyl phosphonates

Cited by 18 publications

References 33 publications

Tunable Approach for the Stereoselective Synthesis of 1-C-Diethylphosphono(difluoromethyl) Iminosugars as Glycosyl Phosphate Mimics

Tunable Approach for the Stereoselective Synthesis of 1-C-Diethylphosphono(difluoromethyl) Iminosugars as Glycosyl Phosphate Mimics

Synthesis of 2‐Substituted Thioglycals from Carbohydrate‐Derived Ketene Dithioacetals

Recent Advances in Synthesis of Difluoromethylene Phosphonates for Biological Applications

Contact Info

Product

Resources

About