Recent advances in transition-metal-catalysed asymmetric coupling reactions with light intervention

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(22), P. 12808 - 12827

Published: Jan. 1, 2021

Transition metal-catalysed asymmetric coupling has been established as a robust tool for constructing complex organic molecules. Although this area extensively studied, the development of efficient protocols to construct stereogenic centres with excellent regio- and enantioselectivities is highly desirable remains challenging. Asymmetric transition metal catalysis light intervention provides practical alternative strategy current methods considerably expands synthetic utility result abundant feedstocks mild conditions. This tutorial review comprehensively summarizes recent advances in transition-metal-catalysed reactions intervention; particular, concise analysis substrate scope mechanistic scenarios governing stereocontrol discussed.

Language: Английский

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Catalytic enantioselective C(sp3)–H functionalization involving radical intermediates

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

Published: Jan. 20, 2021

Abstract Recently, with the boosted development of radical chemistry, enantioselective functionalization C( sp 3 )–H bonds via a pathway has witnessed renaissance. In principle, two distinct catalytic modes, distinguished by steps in which stereochemistry is determined (the formation step or step), can be devised. This Perspective discusses state-of-the-art area involving intermediates as well future challenges and opportunities.

Language: Английский

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Asymmetric three-component olefin dicarbofunctionalization enabled by photoredox and copper dual catalysis

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

Published: March 22, 2021

Abstract The intermolecular three-component alkene vicinal dicarbofunctionalization (DCF) reaction allows installation of two different carbon fragments. Despite extensive investigation into its ionic chemistry, the enantioseletive radical-mediated versions DCF reactions remain largely unexplored. Herein, we report an intermolecular, enantioselective radical olefins enabled by merger addition and cross-coupling using photoredox copper dual catalysis. Key to success this protocol relies on chemoselective acyl cyanoalkyl radicals, generated in situ from redox-active oxime esters a photocatalytic N-centered iminyl radical-triggered C-C bond cleavage event, onto alkenes form new radicals. Single electron metalation such newly formed radicals TMSCN-derived L1 Cu(II)(CN) 2 complex leads asymmetric cross-coupling. This process proceeds under mild conditions, tolerates diverse range functionalities synthetic handles, leading valuable optically active β –cyano ketones alkyldinitriles, respectively, highly manner (>60 examples, up 97% ee).

Language: Английский

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Recent advances in multifunctional nanomaterials for photothermal-enhanced Fenton-based chemodynamic tumor therapy

Materials Today Bio, Journal Year: 2022, Volume and Issue: 13, P. 100197 - 100197

Published: Jan. 1, 2022

Photothermal (PT)-enhanced Fenton-based chemodynamic therapy (CDT) has attracted a significant amount of research attention over the last five years as highly effective, safe, and tumor-specific nanomedicine-based therapy. CDT is new emerging nanocatalyst-based therapeutic strategy for in situ treatment tumors via Fenton reaction or Fenton-like reaction, which got fast progress recent because its high specificity activation by endogenous substances. A variety multifunctional nanomaterials such metal-, metal oxide-, metal-sulfide-based nanocatalysts have been designed constructed to trigger within tumor microenvironment (TME) generate cytotoxic hydroxyl radicals (•OH), efficient killing cells. However, still required enhance curative outcomes minimize side effects. Specifically, efficiency certain CDTs hindered TME, including low levels hydrogen peroxide (H2O2), overexpression reduced glutathione (GSH), catalytic efficacy reactions (pH 5.6-6.8), makes it difficult completely cure cancer using monotherapy. For this reason, photothermal (PTT) utilized combination with efficacy. More interestingly, heating during PTT not only causes damage cells but can also accelerate generation •OH reactions, thus enhancing efficacy, providing more effective when compared Currently, synergistic PT-enhanced both PT properties made enormous theranostics. there no comprehensive review on subject published date. In review, we first summarize treatment. We then discuss potential challenges future development nanocatalytic clinical application.

Language: Английский

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Mechanism-based ligand design for copper-catalysed enantioconvergent C(sp3)–C(sp) cross-coupling of tertiary electrophiles with alkynes

Nature Chemistry, Journal Year: 2022, Volume and Issue: 14(8), P. 949 - 957

Published: May 26, 2022

Language: Английский

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Ligand Development for Copper-Catalyzed Enantioconvergent Radical Cross-Coupling of Racemic Alkyl Halides

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(38), P. 17319 - 17329

Published: Sept. 1, 2022

The enantioconvergent cross-coupling of racemic alkyl halides represents a powerful tool for the synthesis enantioenriched molecules. In this regard, first-row transition metal catalysis provides suitable mechanism stereoconvergence by converting to prochiral radical intermediates owing their good single-electron transfer ability. contrast noble development chiral nickel catalyst, copper-catalyzed is less studied. Besides enantiocontrol issue, major challenge arises from weak reducing capability copper that slows reaction initiation. Recently, significant efforts have been dedicated basic research aimed at developing ligands halides. This perspective will discuss advances in burgeoning area with particular emphasis on strategic anionic ligand design tune initiation under thermal conditions our group.

Language: Английский

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General (hetero)polyaryl amine synthesis via multicomponent cycloaromatization of amines

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 2, 2025

Language: Английский

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Copper‐Catalyzed Asymmetric Coupling of Allenyl Radicals with Terminal Alkynes to Access Tetrasubstituted Allenes

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(4), P. 2160 - 2164

Published: Oct. 14, 2020

In contrast to the wealth of asymmetric transformations for generating central chirality from alkyl radicals, enantiocontrol over allenyl radicals forging axial represents an uncharted domain. The challenge arises unique elongated linear configuration that necessitates stereo-differentiation remote motifs away radical reaction site. We herein describe a copper-catalyzed 1,4-carboalkynylation 1,3-enynes via coupling with terminal alkynes, providing diverse synthetically challenging tetrasubstituted chiral allenes. A N,N,P-ligand is crucial both initiation and highly reactive radicals. features broad substrate scope, covering variety (hetero)aryl alkynes as well precursors excellent functional group tolerance.

Language: Английский

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Photoinduced Copper‐Catalyzed Asymmetric Decarboxylative Alkynylation with Terminal Alkynes

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(39), P. 16926 - 16932

Published: June 25, 2020

Abstract We describe a photoinduced copper‐catalyzed asymmetric radical decarboxylative alkynylation of bench‐stable N‐hydroxyphthalimide(NHP)‐type esters racemic alkyl carboxylic acids with terminal alkynes, which provides flexible platform for the construction chiral C(sp 3 )−C(sp) bonds. Critical to success this process are not only use copper catalyst as dual photo‐ and cross‐coupling but also tuning NHP‐type inhibit facile homodimerization alkyne, respectively. Owing stable easily available esters, reaction features broader substrate scope compared reactions using halide counterparts, covering (hetero)benzyl‐, allyl‐, aminocarbonyl‐substituted acid derivatives, (hetero)aryl well silyl thus providing vital complementary approach previously reported method.

Language: Английский

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Copper-Catalyzed Enantioconvergent Radical Suzuki–Miyaura C(sp³)–C(sp²) Cross-Coupling

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(46), P. 19652 - 19659

Published: Nov. 4, 2020

A copper-catalyzed enantioconvergent Suzuki–Miyaura C(sp3)–C(sp2) cross-coupling of various racemic alkyl halides with organoboronate esters has been established in high enantioselectivity. Critical to the success is use a chiral cinchona alkaloid-derived N,N,P-ligand for not only enhancing reducing capability copper catalyst favor stereoablative radical pathway over stereospecific SN2-type process but also providing an ideal environment achieve challenging enantiocontrol highly reactive species. The reaction broad scope respect both coupling partners, covering aryl- and heteroarylboronate esters, as well benzyl-, heterobenzyl-, propargyl bromides chlorides good functional group compatibility. Thus, it provides expedient access toward range useful enantioenriched skeletons featuring tertiary benzylic stereocenters.

Language: Английский

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