Selective C(sp3)–H arylation/alkylation of alkanes enabled by paired electrocatalysis

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Dec. 2, 2023

We report a combination of electrocatalysis and photoredox catalysis to perform selective C(sp3)-H arylation/alkylation alkanes, in which binary catalytic system based on earth-abundant iron nickel is applied. Reaction selectivity between two-component arylation three-component alkylation tuned by modulating the applied current light source. Importantly, an ultra-low anodic potential (~0.23 V vs. Ag/AgCl) this protocol, thus enabling compatibility with variety functional groups (>70 examples). The robustness method further demonstrated preparative scale late-stage diversification natural products pharmaceutical derivatives.

Language: Английский

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Photoredox catalysis harvesting multiple photon or electrochemical energies

Beilstein Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 19, P. 1055 - 1145

Published: July 28, 2023

Photoredox catalysis (PRC) is a cutting-edge frontier for single electron-transfer (SET) reactions, enabling the generation of reactive intermediates both oxidative and reductive processes via photon activation catalyst. Although this represents significant step towards chemoselective and, more generally, sustainable chemistry, its efficacy limited by energy visible light photons. Nowadays, excellent alternative conditions are available to overcome these limitations, harvesting two different but correlated concepts: use multi-photon such as consecutive photoinduced electron transfer (conPET) combination photo- electrochemistry in synthetic photoelectrochemistry (PEC). Herein, we review most recent contributions fields activations organic functional groups. New opportunities chemists captured, selective reactions employing super-oxidants super-reductants engage unactivated chemical feedstocks, scalability up gram scales continuous flow. This provides comparisons between techniques (multi-photon photoredox PEC) help reader fully understand their similarities, differences potential applications therefore choose which method appropriate given reaction, scale purpose project.

Language: Английский

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Enantioselective Copper-Catalyzed Fukuyama Indole Synthesis from 2-Vinylphenyl Isocyanides

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8665 - 8676

Published: April 8, 2023

Enantioenriched chiral indoles are of high interest for the pharmaceutical and agrochemical industries. Herein, we present an asymmetric Fukuyama indole synthesis through a mild efficient radical cascade reaction to access 2-fluoroalkylated 3-(α-cyanobenzylated) by stereochemical control with copper-bisoxazoline complex using 2-vinylphenyl arylisocyanides as acceptors fluoroalkyl iodides C-radical precursors. Radical addition isonitrile moiety, 5-exo-trig cyclization, Cu-catalyzed stereoselective cyanation provide targeted excellent enantioselectivity good yields. Due similar electronic steric properties two aryl substituents be differentiated, enantioselective construction cyano diaryl methane stereocenter is highly challenging. Mechanistic studies reveal negative nonlinear effect which allows proposing model explain outcome. Scalability potential utility enantioenriched hubs tryptamines, indole-3-acetic acid derivatives, triarylmethanes demonstrated, formal natural product analogue disclosed.

Language: Английский

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Dual Photoredox and Copper Catalysis: Enantioselective 1,2-Amidocyanation of 1,3-Dienes

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(11), P. 7523 - 7528

Published: May 19, 2023

Dual photoredox–transition-metal catalysis has emerged as a powerful tool for the development of chemical transformations. However, its application in selective difunctionalization 1,3-dienes remains essentially unexploited. By synergistic action photoredox and copper catalysts, we report herein an enantioselective 1,2-amidocyanation 1,3-dienes. Visible-light irradiation chloroform solution conjugated dienes, N-Boc-amidopyridinium salts, TMSCN presence catalytic amount fac-Ir(ppy)3, Cu(OTf)2·xH2O, chiral Box ligand affords three-component adducts good to high yields with regio- enantioselectivities. A L*CuCN complex, fully characterized spectroscopically confirmed by X-ray crystallographic analysis, is able catalyze transformation, therefore supporting inner-sphere cyanide transfer pathway.

Language: Английский

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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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