Photoinduced Nonstabilized Azomethine Ylide Formation for the Preparation of Fluorine Containing Pyrrolidines

Thibault, Thierry; Lebargy, Cyril; Pfund, Emmanuel; Lequeux, Thierry

doi:10.1021/acs.joc.9b00244

Cited by 27 publications

(26 citation statements)

References 39 publications

(71 reference statements)

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“…The group of Lequeux used a photoinduced 1,3‐dipolar cycloaddition of azomethine ylide generated from amine 139 to α,α‐difluoroallylphosphonates 140 to developed an efficient synthesis of CF 2 ‐phosphonate‐containing pyrrolidines 141 (Scheme 51B). Organic dye eosin Y was employed as the photocatalyst, promoting the formation of the ylide under green light irradiation and mild reaction conditions, under which α,α‐difluoroallylphosphonates 140 appeared to be excellent dipolarophiles giving pyrrolidines 141 in 70–87% yields [187] . Analogous reactivity of compounds of general formal 140 toward other 1,3‐dipolar species is therefore anticipated.…”

Section: Synthetic Methodsmentioning

confidence: 99%

Recent Advances in Synthesis of Difluoromethylene Phosphonates for Biological Applications

et al. 2021

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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.

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Section: Synthetic Methodsmentioning

confidence: 99%

Recent Advances in Synthesis of Difluoromethylene Phosphonates for Biological Applications

et al. 2021

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“…Recently, Lequeux and co‐workers disclosed a mild and reproducible method for the formation of a nonstabilized azomethine ylide catalyzed with eosin Y under green light irradiation (Scheme 22). [32] The resulting 1,3‐dipole was trapped with 3‐nitroindole to access dearomative adduct hexahydropyrroloindole scaffold.…”

Section: [3+2] Dearomative Annulationmentioning

confidence: 99%

Dearomatization of Nitro(hetero)arenes through Annulation

Wang

Ren

2022

Eur J Org Chem

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Dearomatization reactions employing simple aromatic compounds have showcased remarkable progress in the recent decade and have emerged as one of the most straightforward and powerful tools for the creation of highly functionalized, three-dimensional molecular frameworks commonly encountered in medicinal chemistry and life sciences. Among the aromatic compounds in use, nitro(hetero)arenes, which feature a less pronounced aromatic character due to the presence of highly electron-withdrawing nitro group, have been extensively used in different types of dearomatization reactions. The dearomative annulation reaction serves as a powerful and versatile method for the construction of complex polycyclic systems. This overview presents a brief summary of recent impressive advances in nitro(hetero)arenes dearomative annulation and provides some inspirations for future research.

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“…developed a photocatalyzed reaction for the formation of azomethine ylide 6a, at room temperature, under non-acidic conditions. 10 To this end, they used Eosin Y (EY), an organic dye, to decompose hemiaminal 8a and generate the dipole under green light irradiation. Although the article focuses mainly on the preparation of fluorinated pyrrolidines, the authors included one example of a (3+2) dearomative cycloaddition with N-tosyl-3-nitroindole 1c, which showed excellent conversion of the heteroaromatic substrate under these photocatalyzed conditions (Table 2, entry 8).…”

Section: Introductionmentioning

confidence: 99%