Photoredox streamlines electrocatalysis: photoelectrosynthesis of polycyclic pyrimidin-4-ones through carbocyclization of unactivated alkenes with malonates

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(7), P. 4199 - 4208

Published: Jan. 1, 2024

A new photoelectrocatalytic mode permits the synthesis of polycyclic pyrimidin-4-ones through dehydrogenative cyclization malonates with unactivated alkenes.

Language: Английский

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Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(17), P. 10192 - 10280

Published: Aug. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Language: Английский

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Biomimetic Photoexcited Cobaloxime Catalysis in Organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)

Published: May 22, 2024

Abstract Drawing inspiration from nature has long been a cornerstone of chemical innovation, with natural systems offering wealth untapped potential for discovery. In this minireview, we delve into the burgeoning field cobaloxime catalysis in organic synthesis, which mimics catalytic activity organometallic alkylcobalamine enzymes. Our focus lies on elucidating latest advancements area, as well delineating primary mechanistic pathways at play. By describing, and comparing these mechanisms, provide comprehensive overview current state‐of‐the‐art, while also shedding light key unresolved challenges that await further exploration.

Language: Английский

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Synthesis of Diverse 4‐Pyrrolin‐2‐ones by Electrochemically Induced Dehydrogenative Regioselective Cyclization of 3‐Aza‐1,5‐dienes and 1,3‐Dicarbonyl Compounds

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(11)

Published: Jan. 20, 2024

Abstract A practical and mild electrochemical dehydrogenative regioselective cyclization method has been established for the synthesis of 4‐pyrrolin‐2‐ones using 3‐aza‐1,5‐dienes 1,3‐dicarbonyl compounds as substrates. This protocol is catalyst‐free, metal‐free, does not require oxidizing agents. It exhibits wide substrate compatibility can be easily scaled up to gram scale.

Language: Английский

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Photoinduced Three-Component Carboarylation of Unactivated Alkenes with Protic C(sp³)–H Feedstocks

Organic Letters, Journal Year: 2022, Volume and Issue: 24(41), P. 7677 - 7684

Published: Oct. 10, 2022

A general and mild strategy involving three-component carboarylation of unactivated alkenes with protic C(sp3)–H feedstocks via photoredox catalysis was reported. This catalytic system is compatible a broad range alkenes, cyano-substituted arenes, diverse feedstocks. The synthetic value this protocol demonstrated by the late-stage functionalization complex molecules synthesis antiallergies including pheniramine, chlorpheniramine, brompheniramine.

Language: Английский

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2-Isopropylthioxanthone-Catalyzed Divergent Functionalization of Bicyclo[1.1.0]butanes under Visible-Light Irradiation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(33), P. 6184 - 6188

Published: Aug. 9, 2023

1,3-Functionalized cyclobutane structural motifs are ubiquitous in natural products and pharmaceuticals. Photoinduced alkylation of bicyclo[1.1.0]butanes (BCBs) offers a step-economical strategy for accessing 1,3-functionalized motifs. Herein, we disclose general mild photocatalytic protocol bromoallylation BCBs metal, additive-free manner by using the same photocatalyst, 2-isopropylthioxanthone, different catalytic roles. Furthermore, synthetic utility these was illustrated synthesis various valuable complex derivatives.

Language: Английский

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Visible‐Light Photoredox Catalyzed Regioselective 1,4‐Hydroalkylation of 1,3‐Enyne

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(51)

Published: June 27, 2023

Described herein is a visible-light photoredox-catalyzed regioselective 1,4-hydroalkylation of 1,3-enynes. Various di- and tri-substituent allenes were really accessible under the present reaction conditions. The photoredox activation carbon nucleophile to generate its radical species, allowing addition with un-activated enynes. synthetic utility for protocol was demonstrated by large-scale reaction, as well derivatization allene product.

Language: Английский

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Divergent and Synergistic Photocatalysis: Hydro- and Oxoalkylation of Vinyl Arenes for the Stereoselective Synthesis of Cyclopentanols via a Formal [4+1]-Annulation of 1,3-Dicarbonyls

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(22), P. 14398 - 14407

Published: Nov. 9, 2022

The controllable divergent reactivity of 1,3-dicarbonyls is described, which enables the efficient hydro- and oxoalkylation vinyl arenes. Both reaction pathways are initiated through formation polarity-reversed C-centered-radical intermediates at active methylene center via direct photocatalytic C–H bond transformations. alkenes achieved under aerobic conditions a Cu(II)-photomediated rebound mechanism, while corresponding hydroalkylation becomes possible nitrogen atmosphere by combination 4CzIPN Brønsted base. breadth these protocols demonstrated in late-stage modification drugs natural products transformation to variety heterocycles such as pyridines, pyrroles, or furans. Moreover, two catalytic modes can be combined synergistically for stereoselective construction cyclopentanol derivatives formal [4+1]-annulation process.

Language: Английский

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1,3-Difunctionalization of Alkenes by Cobaloxime Photocatalysis

Organic Letters, Journal Year: 2024, Volume and Issue: 26(32), P. 6809 - 6813

Published: Aug. 5, 2024

Represented herein is the first 1,3-difunctionalization of alkenes via photocatalysis. A single cobaloxime used to carry out two catalytic cycles in which not only as a photocatalyst initiate reaction but also metal catalyst for β-H elimination process. Electron-deficient alkenes, electron-rich and unactivated could be directly converted 1,3-bisphosphorylated products, even unsymmetric with H

Language: Английский

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Photoinduced Cobaloxime-Catalyzed Regio- and Diastereoselective Hydrogen-Evolution C(sp³)–H Phosphorylation of Bicyclo[1.1.0]butanes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 15, 2025

Radical-initiated functionalization of bicyclo[1.1.0]butanes (BCBs) is a straightforward approach to accessing diverse cyclobutane derivatives. However, selective C(sp3)–H at the C2 position BCBs remains scarce. Herein, mild protocol for hydrogen-evolution phosphorylation with enabled by photoinduced cobaloxime catalysis was realized in regio- and diastereoselective manner. This oxidant- additional photocatalyst-free method wide range diarylphosphine oxides. The mechanism studied via control experiments DFT calculation. Moreover, efficiency this highlighted synthesis high-value, structurally complex molecules.

Language: Английский

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