Direct C–H difluoromethylation of heterocycles via organic photoredox catalysis

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: Jan. 31, 2020

Abstract The discovery of modern medicine relies on the sustainable development synthetic methodologies to meet needs associated with drug molecular design. Heterocycles containing difluoromethyl groups are an emerging but scarcely investigated class organofluoro molecules potential applications in pharmaceutical, agricultural and material science. Herein, we developed organophotocatalytic direct difluoromethylation heterocycles using O 2 as a green oxidant. C–H oxidative obviates need for pre-functionalization substrates, metals additives. operationally straightforward method enriches efficient synthesis many difluoromethylated moderate excellent yields. pharmaceutical moleculars demonstrates practicability this methodology late-stage development. Moreover, 2′-deoxy-5-difluoromethyluridine (F TDR) exhibits promising activity against some cancer cell lines, indicating that might provide assistance discovery.

Language: Английский

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Multimetallic-Catalyzed C–C Bond-Forming Reactions: From Serendipity to Strategy

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(12), P. 6596 - 6614

Published: March 13, 2023

The use of two or more metal catalysts in a reaction is powerful synthetic strategy to access complex targets efficiently and selectively from simple starting materials. While capable uniting distinct reactivities, the principles governing multimetallic catalysis are not always intuitive, making discovery optimization new reactions challenging. Here, we outline our perspective on design elements using precedent well-documented C–C bond-forming reactions. These strategies provide insight into synergy compatibility individual components reaction. Advantages limitations discussed promote further development field.

Language: Английский

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Carbon–Carbon Bond Cleavage for Late-Stage Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(22), P. 12313 - 12370

Published: Nov. 9, 2023

Late-stage functionalization (LSF) introduces functional group or structural modification at the final stage of synthesis natural products, drugs, and complex compounds. It is anticipated that late-stage would improve drug discovery's effectiveness efficiency hasten creation various chemical libraries. Consequently, products a productive technique to produce product derivatives, which significantly impacts biology development. Carbon-carbon bonds make up fundamental framework organic molecules. Compared with carbon-carbon bond construction, activation can directly enable molecular editing (deletion, insertion, atoms groups atoms) provide more efficient accurate synthetic strategy. However, selective unstrained still one most challenging projects in synthesis. This review encompasses strategies employed recent years for cleavage by explicitly focusing on their applicability functionalization. expands current discourse reactions providing comprehensive overview types bonds. includes C-C(sp), C-C(sp2), C-C(sp3) single bonds; double triple bonds, focus catalysis transition metals organocatalysts. Additionally, specific topics, such as ring-opening processes involving three-, four-, five-, six-membered rings, are discussed, exemplar applications these techniques showcased context bioactive molecules discovery. aims shed light advancements field propose potential avenues future research realm

Language: Английский

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Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Jan. 29, 2024

Abstract We highlight key contributions in the field of direct radical C Ar − H (hetero)aromatic functionalization involving fluorinated radicals. A compilation Functional Group Transfer Reagents and their diverse activation mechanisms leading to release radicals are discussed. The substrate scope for each is analyzed classified into three categories according electronic properties substrates. Density functional theory computational analysis provides insights chemical reactivity several through electrophilicity nucleophilicity parameters. Theoretical reduction potentials also highlights remarkable correlation between oxidizing ability. It established that highly (e.g. ⋅OCF 3 ) capable engaging single‐electron transfer (SET) processes rather than addition, which good agreement with experimental literature data. scale, based on barrier addition these benzene elaborated using high accuracy DLPNO‐(U)CCSD(T) method.

Language: Английский

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Photoredox-Catalyzed Bromodifluoromethylation of Alkenes with (Difluoromethyl)triphenylphosphonium Bromide

Organic Letters, Journal Year: 2016, Volume and Issue: 18(10), P. 2419 - 2422

Published: May 3, 2016

Under visible-light photoredox conditions, difluoromethyltriphenylphosphonium bromide was used as the precursor of CF2H radical for bromodifluoromethylation alkenes. The presence catalytic CuBr2 resulted in selective formation bromodifluoromethylated products.

Language: Английский

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