Photoredox Catalysis in Organic Chemistry

The Journal of Organic Chemistry, Journal Year: 2016, Volume and Issue: 81(16), P. 6898 - 6926

Published: Aug. 1, 2016

In recent years, photoredox catalysis has come to the forefront in organic chemistry as a powerful strategy for activation of small molecules. general sense, these approaches rely on ability metal complexes and dyes convert visible light into chemical energy by engaging single-electron transfer with substrates, thereby generating reactive intermediates. this Perspective, we highlight unique expedite development completely new reaction mechanisms, particular emphasis placed multicatalytic strategies that enable construction challenging carbon–carbon carbon–heteroatom bonds.

Language: Английский

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Dual Catalysis Strategies in Photochemical Synthesis

Chemical Reviews, Journal Year: 2016, Volume and Issue: 116(17), P. 10035 - 10074

Published: April 25, 2016

The interaction between an electronically excited photocatalyst and organic molecule can result in the genertion of a diverse array reactive intermediates that be manipulated variety ways to synthetically useful bond constructions. This Review summarizes dual-catalyst strategies have been applied synthetic photochemistry. Mechanistically distinct modes photocatalysis are discussed, including photoinduced electron transfer, hydrogen atom energy transfer. We focus upon cooperative interactions photocatalysts with redox mediators, Lewis Brønsted acids, organocatalysts, enzymes, transition metal complexes.

Language: Английский

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Visible light photoredox-controlled reactions of N-radicals and radical ions

Chemical Society Reviews, Journal Year: 2016, Volume and Issue: 45(8), P. 2044 - 2056

Published: Jan. 1, 2016

Radicals are an important class of versatile and highly reactive species. Compared with the wide applications various C-centred radicals, however, N-radical species including N-centred radicals radical ions remain largely unexplored due to lack convenient methods for their generation. In recent years, visible light photoredox catalysis has emerged as a powerful platform generation methodology development towards synthesis diverse N-containing compounds. this tutorial review, we highlight advances in rapidly developing area particular emphases put on working models new reaction design.

Language: Английский

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Carbon–Carbon Bond Forming Reactions via Photogenerated Intermediates

Chemical Reviews, Journal Year: 2016, Volume and Issue: 116(17), P. 9850 - 9913

Published: April 12, 2016

The present review offers an overview of the current approaches for photochemical and photocatalytic generation reactive intermediates their application in formation carbon-carbon bonds. Valuable synthetic targets are accessible, including arylation processes, both carbo- heterocycles, alpha- beta-functionalization carbonyls, addition reactions onto double triple According to recent advancements field visible/solar light catalysis, a significant part literature reported herein involves radical ions radicals as key intermediates, with particular attention most examples. Synthetic carbenes, biradicals/radical pairs carbocations have been also reported.

Language: Английский

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New Strategies for the Transition-Metal Catalyzed Synthesis of Aliphatic Amines

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(5), P. 2613 - 2692

Published: Feb. 17, 2020

Transition-metal catalyzed reactions that are able to construct complex aliphatic amines from simple, readily available feedstocks have become a cornerstone of modern synthetic organic chemistry. In light the ever-increasing importance across range chemical sciences, this review aims provide concise overview transition-metal approaches alkylamine synthesis and their functionalization. Selected examples amine bond forming include: (a) hydroamination hydroaminoalkylation, (b) C(sp3)–H functionalization, (c) visible-light-mediated photoredox catalysis.

Language: Английский

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Catalytic alkylation of remote C–H bonds enabled by proton-coupled electron transfer

Nature, Journal Year: 2016, Volume and Issue: 539(7628), P. 268 - 271

Published: Oct. 12, 2016

Language: Английский

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Synthetic Applications of Proton-Coupled Electron Transfer

Accounts of Chemical Research, Journal Year: 2016, Volume and Issue: 49(8), P. 1546 - 1556

Published: July 29, 2016

ConspectusRedox events in which an electron and proton are exchanged a concerted elementary step commonly referred to as proton-coupled transfers (PCETs). PCETs known operate numerous important biological redox processes, well recent inorganic technologies for small molecule activation. These studies suggest that PCET catalysis might also function general mode of substrate activation organic synthesis. Over the past three years, our group has worked advance this hypothesis demonstrate synthetic utility through development novel catalytic radical chemistries. The central aim these efforts been ability homolytically activate wide variety common functional groups energetically inaccessible using molecular H atom transfer catalysts.To do so, we made use simple formalism first introduced by Mayer co-workers allowed us predict thermodynamic capacity any oxidant/base or reductant/acid pair formally add remove H· from given substrate. With insight, were able rationally select catalyst combinations thermodynamically competent homolyze extraordinarily strong E–H σ-bonds found many protic (BDFEs > 100 kcal/mol) form unusually weak bonds hydrogen via reductive action π-systems < 35 kcal/mol). ideas reduced practice new systems activations ketones oxidative amide N–H directly furnish reactive ketyl amidyl radicals, respectively. In both systems, reaction outcomes be successfully predicted effective bond strength formalism, suggesting thermochemical considerations can provide useful actionable insights into design.The control enantioselectivity free processes established. Specifically, multisite requires formation pre-equilibrium between donor/acceptor prior charge transfer. We recognized H-bond interfaces persist following event, resulting noncovalent complexes nascent intermediates. When chiral donors/acceptors employed, association basis asymmetric induction subsequent bond-forming steps. discuss capitalize on understanding protocol enantioselective aza-pinacol cyclizations.Lastly, highlight alternative mechanism exploits redox-active metals weaken coordinated ligands, enabling nominally ∼ kcal) abstracted acceptors with concomitant oxidation metal center. This "soft homolysis" enables generation metalated intermediates substrates under completely neutral conditions. example is presented context C–N forming jointly mediated bulky titanocene stable nitroxyl TEMPO.

Language: Английский

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New amination strategies based on nitrogen-centered radical chemistry

Chemical Society Reviews, Journal Year: 2016, Volume and Issue: 45(11), P. 3069 - 3087

Published: Jan. 1, 2016

Recent advances in promising metal-catalyzed and visible-light initiated radical amination reactions are reviewed.

Language: Английский

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Amide-directed photoredox-catalysed C–C bond formation at unactivated sp3 C–H bonds

Nature, Journal Year: 2016, Volume and Issue: 539(7628), P. 272 - 275

Published: Oct. 12, 2016

Language: Английский

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Illuminating Photoredox Catalysis

Trends in Chemistry, Journal Year: 2019, Volume and Issue: 1(1), P. 111 - 125

Published: Feb. 23, 2019

Language: Английский

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