Arene dearomatization through a catalytic N-centered radical cascade reaction DOI Creative Commons
Rory C. McAtee, Efrey A. Noten, Corey R. J. Stephenson

et al.

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

Published: May 20, 2020

Abstract Arene dearomatization reactions are an important class of synthetic technologies for the rapid assembly unique chemical architectures. Herein, we report a catalytic protocol to initiate carboamination/dearomatization cascade that proceeds through transient sulfonamidyl radical intermediates formed from native sulfonamide N–H bonds leading 1,4-cyclohexadiene-fused sultams. Importantly, this work demonstrates facile approach employ two-dimensional aromatic compounds as modular building blocks generate richly substituted, three-dimensional compounds. These occur at room temperature under visible light irradiation and catalyzed by combination iridium(III) photocatalyst dialkyl phosphate base. Reaction optimization, substrate scope, mechanistic features, applications transformation presented.

Language: Английский

New Strategies for the Transition-Metal Catalyzed Synthesis of Aliphatic Amines DOI Creative Commons
Aaron Trowbridge, Scarlett M. Walton, Matthew J. Gaunt

et al.

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

Citations

704
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

336
Hantzsch esters: an emerging versatile class of reagents in photoredox catalyzed organic synthesis DOI

Peng‐Zi Wang,

Jia‐Rong Chen, Wen‐Jing Xiao

et al.

Organic & Biomolecular Chemistry, Journal Year: 2019, Volume and Issue: 17(29), P. 6936 - 6951

Published: Jan. 1, 2019

This minireview highlights the recent advances in chemistry of Hantzsch esters photoredox catalyzed organic synthesis, with particular emphasis placed on reaction mechanisms.

Language: Английский

Citations

294
Catalytic Enantioselective Addition of Prochiral Radicals to Vinylpyridines DOI

Kangning Cao,

Siu Min Tan, Richmond Lee

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(13), P. 5437 - 5443

Published: March 13, 2019

Pyridine, one of the most important azaarenes, is ubiquitous in functional molecules. The electronic properties pyridine have been exploited to trigger asymmetric transformations prochiral species as a direct approach for accessing chiral derivatives. However, full potential this synthetic strategy construction enantioenriched γ-functionalized pyridines remains untapped. Here, we describe first enantioselective addition radicals vinylpyridines under cooperative photoredox and catalysis mediated by visible light. reductive couplings with aldehydes, ketones, imines were achieved employing Brønsted acid activate reaction partners provide stereocontrol via H-bonding interactions. Valuable γ-secondary/tertiary hydroxyl- amino-substituted obtained high yields good excellent enantioselectivities.

Language: Английский

Citations

201
Engineering Semiconductor Quantum Dots for Selectivity Switch on High-Performance Heterogeneous Coupling Photosynthesis DOI
Ming–Yu Qi, Marco Conte, Zi‐Rong Tang

et al.

ACS Nano, Journal Year: 2022, Volume and Issue: 16(10), P. 17444 - 17453

Published: Sept. 28, 2022

Semiconductor-based photoredox catalysis brings an innovative strategy for sustainable organic transformation (e.g., C-C/C-X bond formation), via radical coupling under mild conditions. However, since semiconductors interact with photogenerated radicals unselectively, the precise control of selectivity such synthesis by steering conversion is extremely challenging. Here, judicious design a structurally well-defined and atomically dispersed cocatalyst over semiconductor quantum dots, we demonstrate switch on high-performance selective heterogeneous photosynthesis C-C or C-N along hydrogen production Ni-oxo cluster single Pd atom-decorated CdS dots crafted onto SiO2 support. Mechanistic studies unveil that Ph(•CH)NH2 PhCH2NH2•+ act as dominant intermediates divergent coupled vicinal diamines imines, respectively enabled clusters assisted radical-radical atom-assisted addition-elimination. This work overcomes pervasive difficulties regulation in semiconductor-based photochemical synthesis, highlighting vista utilizing cocatalysts active sites to maneuver unselective engineering toward photosynthesis.

Language: Английский

Citations

171
Ynamide Smiles Rearrangement Triggered by Visible-Light-Mediated Regioselective Ketyl–Ynamide Coupling: Rapid Access to Functionalized Indoles and Isoquinolines DOI
Ze‐Shu Wang,

Yang‐Bo Chen,

Hao‐Wen Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(7), P. 3636 - 3644

Published: Jan. 31, 2020

In the past decades, significant advances have been made on radical Smiles rearrangement. However, eventually formed intermediates in these reactions are limited to amidyl radical, except for few examples initiated by a N-centered radical. Here, novel and practical rearrangement triggered photoredox-catalyzed regioselective ketyl-ynamide coupling is reported, which represents first of ynamides. This method enables facile access variety valuable 2-benzhydrylindoles with broad substrate scope generally good yields under mild reaction conditions. addition, this chemistry can also be extended divergent synthesis versatile 3-benzhydrylisoquinolines through similar rearrangement, followed dehydrogenative oxidation. Moreover, such an ynamide intermolecular photoredox catalysis via addition external sources achieved. By control experiments, was shown proceed key ketyl α-imino carbon intermediates.

Language: Английский

Citations

167
Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency DOI
Guglielmo Coppola, Serena Pillitteri, Erik V. Van der Eycken

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(6), P. 2313 - 2382

Published: Jan. 1, 2022

Visible-light photoredox catalysis has been regarded as an extremely powerful tool in organic chemistry, bringing the spotlight back to radical processes. The versatility of photocatalyzed reactions already demonstrated be effective providing alternative routes for cross-coupling well multicomponent reactions. photocatalyst allows generation high-energy intermediates through light irradiation rather than using highly reactive reagents or harsh reaction conditions. In a similar vein, electrochemistry experienced fruitful renaissance generating without need any catalyst. Such milder approaches pose basis toward higher selectivity and broader applicability. electrochemical reactions, species acts starter cascade events. This diverse reactivity use is usually not covered by classical methods. Owing availability cheaper more standardized photo- reactors, easily scalable flow-setups, it surprising that these two fields have become areas increased research interest. Keeping view, this review aimed at overview synthetic design MCRs involving and/or activation crucial step with particular focus on choice difunctionalized reagent.

Language: Английский

Citations

167
Spatial separation of photogenerated carriers and enhanced photocatalytic performance on Ag3PO4 catalysts via coupling with PPy and MWCNTs DOI
Yan Lin, Xin Wu, Yi Han

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2019, Volume and Issue: 258, P. 117969 - 117969

Published: July 20, 2019

Language: Английский

Citations

158
Catalytic asymmetric reductive hydroalkylation of enamides and enecarbamates to chiral aliphatic amines DOI Creative Commons
Jia-Wang Wang, Yan Li, Wan Nie

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Feb. 26, 2021

Abstract To increase the reliability and success rate of drug discovery, efforts have been made to C( sp 3 ) fraction avoid flat molecules. -Rich enantiopure amines are most frequently encountered as chiral auxiliaries, synthetic intermediates for pharmaceutical agents bioactive natural products. Streamlined construction aliphatic has long regarded a paramount challenge. Mainstream approaches, including hydrogenation enamines imines, C–H amination, alkylation were applied synthesis with circumscribed skeleton structures; typically, carbon centre was adjacent an auxiliary aryl or ester group. Herein, we report mild general nickel-catalysed asymmetric reductive hydroalkylation effectively convert enamides enecarbamates into drug-like α-branched derivatives. This reaction involves regio- stereoselective hydrometallation enamide enecarbamate generate catalytic amount enantioenriched alkylnickel intermediate, followed by C–C bond formation via alkyl electrophiles.

Language: Английский

Citations

145
α-Amino Radicals via Photocatalytic Single-Electron Reduction of Imine Derivatives DOI
Jamie A. Leitch, Thomas Rossolini, Tatiana Rogova

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(3), P. 2009 - 2025

Published: Jan. 21, 2020

The construction and manipulation of amine-containing architectures is importance to academic industrial development discovery programs. photochemical single-electron reduction imine derivatives generate α-amino radical intermediates has emerged as a powerful umpolung strategy for opening up underexplored routes such amine motifs. Furthermore, these radicals have been shown engage in wide variety chemistry, including radical–radical coupling, addition electrophiles, reductive amination chemistry. concept also begun see application iminium ion the extension enantiocontrolled C–C bond formation. This Perspective covers recent efforts this synthetic simple complex structures alike.

Language: Английский

Citations

144