Photoredox-Catalyzed Radical Cascade Reaction To Synthesize Fluorinated Pyrrolo[1,2-<i>d</i>]benzodiazepine Derivatives

Lian, Guifang; Li, Jingyu; Liu, Ping; Sun, Peipei

doi:10.1021/acs.joc.9b00937

Cited by 19 publications

(14 citation statements)

References 38 publications

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“…Concerning the reaction pathway, it is not clear yet. However, based on the above experimental results and literatures, [ 24‐31 ] difluoromethylene carbene was involved as the key intermediate.…”

Section: Resultsmentioning

confidence: 73%

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Base‐Promoted Formylation and N‐Difluoromethylation of Azaindoles with Ethyl Bromodifluoroacetate as a Carbon Source

Sun

Zhang

et al. 2021

Chin. J. Chem.

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Azaindoles | C1 building blocks | Difluoromethylene | Hydrolysis | Synthetic methodsWe reported for the first time that ethyl bromodifluoroacetate directly reacts with azaindole without transition metal catalysis to produce a difluoromethyl protected 5-aldehyde group product in one step. It is worth mentioning that the reacted aldehyde group is only formed at the 5 position. In addition, this method has good substrate applicability and functional group tolerance. Finally, we also carried out some mechanism auxiliary experiments, which confirmed that the aldehyde-based carbon comes from ethyl bromodifluoroacetate.

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Section: Resultsmentioning

confidence: 73%

“…How to efficiently convert it into refined products is an important scientific problem. There are already very good methods to convert it into an ester, [ 25 ] a monofluoride reagent, [ 26 ] a carbon group, [ 27 ] a α‐bromide, [ 28 ] a carbonyl group, [ 29 ] etc . (Scheme 1).…”

Section: Background and Originality Contentmentioning

confidence: 99%

Base‐Promoted Formylation and N‐Difluoromethylation of Azaindoles with Ethyl Bromodifluoroacetate as a Carbon Source

Sun

Zhang

et al. 2021

Chin. J. Chem.

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“…In this cycle, the regioselective radical addition to a broad scope of 2‐(1H‐pyrrol‐1‐yl) anilines or indole‐functionalized anilines was induced by single electron transfer (SET) between the excited state photocatalyst fac‐Ir(ppy) 3 and ethyl bromodifluoroacetate, which was further trailed by another SET cycle and intramolecular amidation (Scheme 174). [192] …”

Section: Photochemical Methods Of C−h Functionalizationmentioning

confidence: 99%

Recent Advances in Functionalization of Pyrroles and their Translational Potential

Hunjan

Panday

Gupta

et al. 2021

The Chemical Record

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Among the known aromatic nitrogen heterocycles, pyrrole represents a privileged aromatic heterocycle ranging its occurrence in the key component of “pigments of life” to biologically active natural products to active pharmaceuticals. Pyrrole being an electron‐rich heteroaromatic compound, its predominant functionalization is legendary to aromatic electrophilic substitution reactions. Although a few excellent reviews on the functionalization of pyrroles including the reports by Baltazzi in 1963, Casiraghi and Rassu in 1995, and Banwell in 2006 are available, they are fragmentary and over fifteen years old, and do not cover the modern aspects of catalysis. A review covering a comprehensive package of direct functionalization on pyrroles via catalytic and non‐catalytic methods including their translational potential is described. Subsequent to statutory yet concise introduction, the classical functionalization on pyrroles using Lewis acids largely following an ionic mechanism is discussed. The subsequent discussion follows the various metal‐catalyzed C−H functionalization on pyrroles, which are otherwise difficult to implement by Lewis acids. A major emphasize is given on the radical based pyrrole functionalization under metal‐free oxidative conditions, which is otherwise poorly highlighted in the literature. Towards the end, the current development of pyrrole functionalization under photocatalyzed and electrochemical conditions is appended. Only a selected examples of substrates and important mechanisms are discussed for different methods highlighting their scopes and limitations. The aromatic nucleophillic substitution on pyrroles (being an electron‐rich heterocycle) happened to be the subject of recent investigations, which has also been covered accentuating their underlying conceptual development. Despite great achievements over the past several years in these areas, many challenges and problems are yet to be solved, which are all discussed in summary and outlook.

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“…The Sun group found that 2-(1H-pyrrol-1-yl)anilines and 2-(1H-indol-1-yl)anilines were also good substrates to react with bromodifluoroacetate, providing various fluorinated pyrrolo[1,2-d]benzodiazepine derivatives. 196 Because of the steric disadvantage as well as entropy, the use of aryl-substituted anilines for this difluoromethylation transformation was challenging. The Li group realized the copper-catalyzed C-H [3 + 2] annulation of N-aryl-or alkyl-substituted anilines with bromodifluoroacetate (Scheme 101).…”

Section: Difluoroalkylation With Arenementioning

confidence: 99%

Promising reagents for difluoroalkylation

et al. 2020

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Photoredox-Catalyzed Radical Cascade Reaction To Synthesize Fluorinated Pyrrolo[1,2-d]benzodiazepine Derivatives

Cited by 19 publications

References 38 publications

Base‐Promoted Formylation and N‐Difluoromethylation of Azaindoles with Ethyl Bromodifluoroacetate as a Carbon Source

Base‐Promoted Formylation and N‐Difluoromethylation of Azaindoles with Ethyl Bromodifluoroacetate as a Carbon Source

Recent Advances in Functionalization of Pyrroles and their Translational Potential

Promising reagents for difluoroalkylation

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