Hydrogen Atom Transfer Reactions via Photoredox Catalyzed Chlorine Atom Generation DOI
Samantha Rohe,

Avery O. Morris,

Terry McCallum

et al.

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(48), P. 15664 - 15669

Published: Oct. 8, 2018

Abstract The selective functionalization of chemically inert C−H bonds remains to be fully realized in achieving organic transformations that are redox‐neutral, waste‐limiting, and atom‐economical. catalytic generation chlorine atoms from chloride ions is one the most challenging redox processes, where requirement harsh oxidizing reaction conditions renders it seldom utilized synthetic applications. We report mild, controlled, as a new opportunity for access wide variety hydrogen atom transfer (HAT) reactions owing high stability HCl. discovery photoredox mediated with Ir‐based polypyridyl complex, [Ir(dF(CF 3 )ppy) 2 (dtbbpy)]Cl, under blue LED irradiation reported.

Language: Английский

Synthetic Methods Driven by the Photoactivity of Electron Donor–Acceptor Complexes DOI Creative Commons
Giacomo E. M. Crisenza, Daniele Mazzarella, Paolo Melchiorre

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(12), P. 5461 - 5476

Published: March 5, 2020

The association of an electron-rich substrate with electron-accepting molecule can generate a new molecular aggregate in the ground state, called electron donor-acceptor (EDA) complex. Even when two precursors do not absorb visible light, resulting EDA complex often does. In 1952, Mulliken proposed quantum-mechanical theory to rationalize formation such colored complexes. However, and besides few pioneering studies 20th century, it is only past years that photochemistry has been recognized as powerful strategy for expanding potential visible-light-driven radical synthetic chemistry. Here, we explain why this photochemical approach was overlooked so long. We critically discuss historical context, scientific reasons, serendipitous observations, landmark discoveries were essential progress field. also outline future directions identify key advances are needed fully exploit photochemistry.

Language: Английский

Citations

878

Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C–H Bonds Elaboration DOI Creative Commons
Luca Capaldo, Davide Ravelli, Maurizio Fagnoni

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1875 - 1924

Published: Aug. 6, 2021

Direct photocatalyzed hydrogen atom transfer (d-HAT) can be considered a method of choice for the elaboration aliphatic C–H bonds. In this manifold, photocatalyst (PCHAT) exploits energy photon to trigger homolytic cleavage such bonds in organic compounds. Selective bond may achieved by judicious abstractor (key parameters are electronic character and molecular structure), as well reaction additives. Different classes PCsHAT available, including aromatic ketones, xanthene dyes (Eosin Y), polyoxometalates, uranyl salts, metal-oxo porphyrin tris(amino)cyclopropenium radical dication. The processes (mainly C–C formation) most cases carried out under mild conditions with help visible light. aim review is offer comprehensive survey synthetic applications d-HAT.

Language: Английский

Citations

809

Mechanistic Studies in Photocatalysis DOI Open Access
Luca Buzzetti, Giacomo E. M. Crisenza, Paolo Melchiorre

et al.

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(12), P. 3730 - 3747

Published: Oct. 19, 2018

Abstract The fast‐moving fields of photoredox and photocatalysis have recently provided fresh opportunities to expand the potential synthetic organic chemistry. Advances in light‐mediated processes mainly been guided so far by empirical findings quest for reaction invention. general perception, however, is that entering a more mature phase where combination experimental mechanistic studies will play dominant role sustaining further innovation. This Review outlines key consider when developing photochemical process, best techniques available acquiring relevant information. discussion use selected case highlight how investigations can be instrumental guiding invention development synthetically useful photocatalytic transformations.

Language: Английский

Citations

761

Technological Innovations in Photochemistry for Organic Synthesis: Flow Chemistry, High-Throughput Experimentation, Scale-up, and Photoelectrochemistry DOI
Laura Buglioni, Fabian Raymenants, Aidan Slattery

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2752 - 2906

Published: Aug. 10, 2021

Photoinduced chemical transformations have received in recent years a tremendous amount of attention, providing plethora opportunities to synthetic organic chemists. However, performing photochemical transformation can be quite challenge because various issues related the delivery photons. These challenges barred widespread adoption steps industry. past decade, several technological innovations led more reproducible, selective, and scalable photoinduced reactions. Herein, we provide comprehensive overview these exciting advances, including flow chemistry, high-throughput experimentation, reactor design scale-up, combination photo- electro-chemistry.

Language: Английский

Citations

540

Catalytic enantioselective Minisci-type addition to heteroarenes DOI Open Access
Rupert S. J. Proctor, Holly J. Davis, Robert J. Phipps

et al.

Science, Journal Year: 2018, Volume and Issue: 360(6387), P. 419 - 422

Published: April 5, 2018

Basic heteroarenes are a ubiquitous feature of pharmaceuticals and bioactive molecules, Minisci-type additions radical nucleophiles leading method for their elaboration. Despite many protocols that result in the formation stereocenters, exerting control over absolute stereochemistry at these centers remains an unmet challenge. We report process addition prochiral radicals, generated from amino acid derivatives, to pyridines quinolines. Our offers excellent both enantioselectivity regioselectivity. An enantiopure chiral Brønsted catalyst serves activate substrate induce asymmetry, while iridium photocatalyst mediates required electron transfer processes. anticipate this will expedite access enantioenriched small-molecule building blocks bearing versatile basic heterocycles.

Language: Английский

Citations

459

Generation of Alkyl Radicals: From the Tyranny of Tin to the Photon Democracy DOI Creative Commons
Stefano Crespi, Maurizio Fagnoni

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(17), P. 9790 - 9833

Published: Aug. 6, 2020

Alkyl radicals are key intermediates in organic synthesis. Their classic generation from alkyl halides has a severe drawback due to the employment of toxic tin hydrides point that "flight tyranny tin" radical processes was considered for long time an unavoidable issue. This review summarizes main alternative approaches unstabilized radicals, using photons as traceless promoters. The recent development photochemical and photocatalyzed enabled discovery plethora new precursors, opening world chemistry broader community, thus allowing era photon democracy.

Language: Английский

Citations

359

Chemistry glows green with photoredox catalysis DOI Creative Commons
Giacomo E. M. Crisenza, Paolo Melchiorre

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

Published: Feb. 6, 2020

Can organic chemistry mimic nature in efficiency and sustainability? Not yet, but recent developments photoredox catalysis animated the synthetic field, providing greener opportunities for industry academia.

Language: Английский

Citations

338

Photocatalytic Late-Stage C–H Functionalization DOI
Peter Bellotti, Huan‐Ming Huang,

Teresa Faber

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4237 - 4352

Published: Jan. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Language: Английский

Citations

324

Asymmetric organocatalysis: an enabling technology for medicinal chemistry DOI
Bo Han, Xiang‐Hong He, Yanqing Liu

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(3), P. 1522 - 1586

Published: Jan. 1, 2021

This review provides a comprehensive overview of the recent applications organocatalytic strategies in pharmaceutical synthesis, with focus on preparation antiviral, anticancer, neuroprotective, cardiovascular, antibacterial and antiparasitic agents.

Language: Английский

Citations

320

Chiral Photocatalyst Structures in Asymmetric Photochemical Synthesis DOI
Matthew J. Genzink, Jesse B. Kidd, Wesley B. Swords

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1654 - 1716

Published: Oct. 4, 2021

Asymmetric catalysis is a major theme of research in contemporary synthetic organic chemistry. The discovery general strategies for highly enantioselective photochemical reactions, however, has been relatively recent development, and the variety photoreactions that can be conducted stereocontrolled manner consequently somewhat limited. photocatalysis complicated by short lifetimes high reactivities characteristic photogenerated reactive intermediates; design catalyst architectures provide effective enantiodifferentiating environments these intermediates while minimizing participation uncontrolled racemic background processes proven to key challenge progress this field. This review provides summary chiral structures have studied solution-phase asymmetric photochemistry, including sensitizers, inorganic chromophores, soluble macromolecules. While some photocatalysts are derived from privileged both ground-state transformations, others structural designs unique offer insight into logic required photocatalysis.

Language: Английский

Citations

307