A general asymmetric copper-catalysed Sonogashira C(sp3)–C(sp) coupling

Nature Chemistry, Journal Year: 2019, Volume and Issue: 11(12), P. 1158 - 1166

Published: Oct. 21, 2019

Language: Английский

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Cu-Catalyzed Asymmetric Borylative Cyclization of Cyclohexadienone-Containing 1,6-Enynes

Journal of the American Chemical Society, Journal Year: 2013, Volume and Issue: 135(32), P. 11700 - 11703

Published: July 26, 2013

The first Cu-catalyzed asymmetric borylative cyclization of cyclohexadienone-containing 1,6-enynes is achieved through a tandem process: selective β-borylation propargylic ether and subsequent conjugate addition to cyclohexadienone. reaction proceeds with excellent regioselectivity enantioselectivity afford an optically pure cis-hydrobenzofuran framework bearing alkenylboronate enone substructures. Furthermore, the resulting bicyclic products could be converted bridged tricyclic ring structures. This method extends realm reactions using bis(pinacolato)diboron (B2pin2).

Language: Английский

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Copper-Promoted Functionalization of Organic Molecules: from Biologically Relevant Cu/O₂ Model Systems to Organometallic Transformations

Chemical Reviews, Journal Year: 2019, Volume and Issue: 119(4), P. 2954 - 3031

Published: Jan. 30, 2019

Copper is one of the most abundant and less toxic transition metals. Nature takes advantage bioavailability rich redox chemistry Cu to carry out oxygenase oxidase organic transformations using O2 (or H2O2) as oxidant. Inspired by reactivity these Cu-dependent metalloenzymes, chemists have developed synthetic protocols functionalize molecules under enviormentally benign conditions. also promotes other usually catalyzed 4d 5d metals (Pd, Pt, Rh, etc.) such nitrene insertions or C–C C–heteroatom coupling reactions. In this review, we summarized relevant research in which copper catalyzes functionalization molecules, including biological catalysis, bioinspired model systems, organometallic reactivity. The reaction mechanisms processes take place are discussed detail.

Language: Английский

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Multifunctional organoboron compounds for scalable natural product synthesis

Nature, Journal Year: 2014, Volume and Issue: 513(7518), P. 367 - 374

Published: Sept. 1, 2014

Language: Английский

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Copper(I)-Catalyzed Borylative exo-Cyclization of Alkenyl Halides Containing Unactivated Double Bond

Journal of the American Chemical Society, Journal Year: 2013, Volume and Issue: 135(7), P. 2635 - 2640

Published: Jan. 27, 2013

A borylative exo-cyclization of alkenyl halides has been reported. The reaction includes the regioselective addition a borylcopper(I) intermediate to unactivated terminal alkenes, followed by intramolecular substitution resulting alkylcopper(I) moiety for halide leaving groups. Experimental and theoretical investigations mechanism have also described. This provides new method synthesis alkylboronates containing strained cycloalkyl structures from simple starting materials.

Language: Английский

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Copper-Catalyzed Radical 1,4-Difunctionalization of 1,3-Enynes with Alkyl Diacyl Peroxides and N-Fluorobenzenesulfonimide

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 141(1), P. 548 - 559

Published: Dec. 4, 2018

Many reactions involving allenyl ion species have been studied, but radicals are less well understood, perhaps because of the inconvenience associated with generation short-lived radicals. We describe here a versatile method for and their previously unreported applications in intermolecular 1,4-carbocyanation 1,4-sulfimidocyanation 1,3-enynes. With assistance trifunctional reagents, alkyl diacyl peroxides or N-fluorobenzenesulfonimide, range synthetically challenging multisubstituted allenes can be prepared high regioselectivity. These easily transformed into useful structures such as fluorinated vinyl cyanides, lactones, functionalized amides, 1-aminonaphthalenes, pyridin-2(1H)-ones, several novel transformations reported. The results radical scavenger clock experiments consistent proposed pathway. Density functional theory (DFT) IR spectroscopy studies suggest formation an isocyanocopper(II) ligand exchange step. On basis IR, DFT, diastereoselectivity studies, isocyanocopper(II)/copper(I) catalytic cycle is proposed, which differs from considered Cu(III) mechanism cyanation reactions.

Language: Английский

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Photoinduced Copper-Catalyzed Asymmetric C–O Cross-Coupling

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(33), P. 13382 - 13392

Published: Aug. 10, 2021

The construction of carbon–heteroatom bonds is one the most active areas research in organic chemistry because function molecules often derived from presence heteroatoms. Although considerable advances have recently been achieved radical-involved catalytic asymmetric C–N bond formation, there has little progress corresponding C–O bond-forming processes. Here, we describe a photoinduced copper-catalyzed cross-coupling readily available oxime esters and 1,3-dienes to generate diversely substituted allylic with high regio- enantioselectivity (>75 examples; up 95% ee). reaction proceeds at room temperature under excitation by purple light-emitting diodes (LEDs) features use single, earth-abundant copper-based chiral catalyst as both photoredox for radical generation source induction coupling. Combined experimental density functional theory (DFT) computational studies suggest formation π-allylcopper complexes redox-active bifunctional reagents through radical–polar crossover process.

Language: Английский

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Beyond classical sulfone chemistry: metal- and photocatalytic approaches for C–S bond functionalization of sulfones

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(15), P. 6774 - 6823

Published: Jan. 1, 2022

Sulfones are excellent candidates for the design of new C–C and C–X bond-forming reactions owing to easy activation C–S bonds. This review focuses on challenges recent opportunities catalytic functionalization sulfones.

Language: Английский

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Oxidative addition of an alkyl halide to form a stable Cu(III) product

Science, Journal Year: 2023, Volume and Issue: 381(6662), P. 1072 - 1079

Published: Sept. 7, 2023

The step that cleaves the carbon-halogen bond in copper-catalyzed cross-coupling reactions remains ill defined because of multiple redox manifolds available to copper and instability high-valent product formed. We report oxidative addition α-haloacetonitrile ionic neutral copper(I) complexes form previously elusive but here fully characterized copper(III) complexes. stability these stems from strong Cu−CF 3 high barrier for C( CF )−C( CH 2 CN ) bond-forming reductive elimination. mechanistic studies we performed suggest proceeds by means two different pathways: an S N 2-type substitution complex a halogen-atom transfer complex. observed pronounced ligand acceleration addition, which correlates with couplings azoles, amines, or alkynes alkyl electrophiles.

Language: Английский

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Site- and Enantioselective Formation of Allene-Bearing Tertiary or Quaternary Carbon Stereogenic Centers through NHC–Cu-Catalyzed Allylic Substitution

Journal of the American Chemical Society, Journal Year: 2012, Volume and Issue: 134(3), P. 1490 - 1493

Published: Jan. 3, 2012

Catalytic enantioselective allylic substitutions that result in addition of an allenyl group (<2% propargyl addition) and formation tertiary or quaternary C–C bonds are described. Commercially available allenylboronic acid pinacol ester is used. Reactions promoted by a 5.0–10 mol % loading sulfonate-bearing chiral bidentate N-heterocyclic carbene (NHC) complexes copper, which exhibit the unique ability to furnish products arising from SN2′ mode addition. Allenyl-containing generated up 95% yield, >98% selectivity, 99:1 enantiomeric ratio (er). Site-selective NHC–Cu-catalyzed hydroboration enantiomerically enriched allenes conversion corresponding β-vinyl ketones demonstrates method's utility.

Language: Английский

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