Switchable Divergent Synthesis Using Photocatalysis DOI
Yota Sakakibara, Kei Murakami

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(3), P. 1857 - 1878

Published: Jan. 20, 2022

A highly selective and divergent synthesis enables access to various molecules has garnered broad interest from not only organic chemists but also medicinal biologists who work with chemical libraries. Since the 20th century, such transformations have been achieved using transition-metal-catalyzed reactions, in which choice of catalyst or ligand crucially affects selectivity. Over past several decades, photocatalysts attracted a considerable amount attention because they provide additional ways control reaction intermediates product selectivity via electron energy transfer. From this perspective, we highlight recent development switchable syntheses photocatalysts, are difficult achieve classical catalytic transformations.

Language: Английский

Visible Light-Driven Radical-Mediated C–C Bond Cleavage/Functionalization in Organic Synthesis DOI
Xiaoye Yu, Jia‐Rong Chen, Wen‐Jing Xiao

et al.

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(1), P. 506 - 561

Published: May 29, 2020

Thermal C–C bond cleavage reactions allow the construction of structurally diverse molecular skeletons via predictable and efficient reorganizations. Visible light photoredox-catalyzed radical-mediated have recently emerged as a powerful alternative method for overcoming thermodynamic kinetic barrier in scaffolds. In recent years, plethora elegant useful been invented, products are sometimes otherwise inaccessible by classic thermal reactions. Considering great influence synthetic potential these reactions, we provide summary state art visible light-driven cleavage/functionalization strategies with specific emphasis on working models. We hoped that this review will be medicinal organic chemists inspire further reaction development interesting area.

Language: Английский

Citations

859

Photoredox-Catalyzed C–H Functionalization Reactions DOI

Natalie Holmberg‐Douglas,

David A. Nicewicz

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1925 - 2016

Published: Sept. 29, 2021

The fields of C–H functionalization and photoredox catalysis have garnered enormous interest utility in the past several decades. Many different scientific disciplines relied on strategies including natural product synthesis, drug discovery, radiolabeling, bioconjugation, materials, fine chemical synthesis. In this Review, we highlight use reactions. We separate review into inorganic/organometallic catalysts organic-based catalytic systems. Further subdivision by reaction class─either sp2 or sp3 functionalization─lends perspective tactical for these methods synthetic applications.

Language: Английский

Citations

635

Remote C–H Functionalization via Selective Hydrogen Atom Transfer DOI
David A. Nagib,

Leah M. Stateman,

Kohki M. Nakafuku

et al.

Synthesis, Journal Year: 2018, Volume and Issue: 50(08), P. 1569 - 1586

Published: Feb. 12, 2018

The selective functionalization of remote C–H bonds via intramolecular hydrogen atom transfer (HAT) is transformative for organic synthesis. This radical-mediated strategy provides access to novel reactivity that complementary closed-shell pathways. As modern methods mild generation radicals are continually developed, inherent selectivity paradigms HAT mechanisms offer unparalleled opportunities developing new strategies functionalization. review outlines the history, recent advances, and mechanistic underpinnings as a guide addressing ongoing challenges in this arena. 1 Introduction 2 Nitrogen-Centered Radicals 2.1 sp3 N-Radical Initiation 2.2 sp2 3 Oxygen-Centered 3.1 Carbonyl Diradical 3.2 Alkoxy Radical 3.3 Non-alkoxy 4 Carbon-Centered 4.1 C-Radical 4.2 5 Conclusion

Language: Английский

Citations

417

Toolbox for Distal C–H Bond Functionalizations in Organic Molecules DOI

Soumya Kumar Sinha,

Srimanta Guin,

Sudip Maiti

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(6), P. 5682 - 5841

Published: Oct. 18, 2021

Transition-metal-catalyzed C–H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted take help this methodology plan their synthetic discourses. This paradigm shift helped in development industrial units as well, making synthesis natural products and pharmaceutical drugs step-economical. In vast zone bond activation, functionalization proximal bonds gained utmost popularity. Unlike bonds, distal is more strenuous requires distinctly specialized techniques. review, we compiled various methods adopted functionalize mechanistic insights within each these procedures, scope methodology. With give complete overview expeditious progress made field organic chemistry while also highlighting its pitfalls, thus leaving open for further modifications.

Language: Английский

Citations

380

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

Photoinduced Remote Functionalisations by Iminyl Radical Promoted C−C and C−H Bond Cleavage Cascades DOI Creative Commons
Elizabeth M. Dauncey, Sara P. Morcillo, James J. Douglas

et al.

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 57(3), P. 744 - 748

Published: Nov. 8, 2017

Abstract A photoinduced cascade strategy leading to a variety of differentially functionalised nitriles and ketones has been developed. These reactions rely on the oxidative generation iminyl radicals from simple oximes. Radical transposition by C(sp 3 )−(sp ) )−H bond cleavage gives access distal carbon that undergo S H 2 functionalisations. mild, visible‐light‐mediated procedures can be used for remote fluorination, chlorination, azidation, were applied modification bioactive structurally complex molecules.

Language: Английский

Citations

357

Visible light photocatalysis in the late-stage functionalization of pharmaceutically relevant compounds DOI
Rolando Cannalire, Sveva Pelliccia, Luca Sancineto

et al.

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 50(2), P. 766 - 897

Published: Dec. 22, 2020

Recent developments and future prospects of visible-light photocatalysis in the late-stage functionalization pharmaceuticals natural bioactive compounds.

Language: Английский

Citations

333

Cleavage of carbon–carbon bonds by radical reactions DOI
Paramasivam Sivaguru, Zikun Wang, Giuseppe Zanoni

et al.

Chemical Society Reviews, Journal Year: 2019, Volume and Issue: 48(9), P. 2615 - 2656

Published: Jan. 1, 2019

This review provides insights into thein situgenerated radicals triggered carbon–carbon bond cleavage reactions.

Language: Английский

Citations

321

Photocatalysis in the Life Science Industry DOI
Lisa Candish,

Karl D. Collins,

Gemma C. Cook

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2907 - 2980

Published: Sept. 24, 2021

In the pursuit of new pharmaceuticals and agrochemicals, chemists in life science industry require access to mild robust synthetic methodologies systematically modify chemical structures, explore novel space, enable efficient synthesis. this context, photocatalysis has emerged as a powerful technology for synthesis complex often highly functionalized molecules. This Review aims summarize published contributions field from industry, including research industrial-academic partnerships. An overview developed strategic applications synthesis, peptide functionalization, isotope labeling, both DNA-encoded traditional library is provided, along with summary state-of-the-art photoreactor effective upscaling photocatalytic reactions.

Language: Английский

Citations

292

Visible light photoredox-catalysed remote C–H functionalisation enabled by 1,5-hydrogen atom transfer (1,5-HAT) DOI
Wei‐Si Guo, Qian Wang, Jieping Zhu

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(13), P. 7359 - 7377

Published: Jan. 1, 2021

The generation of heteroatom-centred radicals followed by intramolecular 1,5-HAT and functionalisation the translocated carbon-centred radical is an efficient way to functionalize chemo- regio-selectively remote unactivated C(sp3)–H bond.

Language: Английский

Citations

291