Catalytic three-component dicarbofunctionalization reactions involving radical capture by nickel

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(19), P. 10836 - 10856

Published: Jan. 1, 2021

The catalytic dicarbofunctionalization of unsaturated π bonds represents a powerful platform for the rapid construction complex motifs. Despite remarkable progress, novel and efficient methods achieving such transformations under milder conditions with chemo-, regio-, stereoselectivity still remain significant challenge; thus, their development is highly desirable. Recently, merging nickel catalysis radical chemistry offers new benign unprecedented reactivity selectivity. In this review, we summarize recent advances in area by underpinning domino involving capture to provide clear overview reaction designs mechanistic scenarios.

Language: Английский

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Recent developments on 1,2-difunctionalization and hydrofunctionalization of unactivated alkenes and alkynes involving C–S bond formation

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(5), P. 1322 - 1345

Published: Jan. 1, 2023

Functionalization of alkenes/alkynes is a highly effective route to achieve molecular complexity. This review summarizes recent progresses on the 1,2-difunctionalization/hydrofunctionalization unactivated with C−S bond formation.

Language: Английский

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Ligand-controlled stereodivergent alkenylation of alkynes to access functionalized trans- and cis-1,3-dienes

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

Published: Jan. 4, 2023

Precise stereocontrol of functionalized alkenes represents a long-standing research topic in organic synthesis. Nevertheless, the development catalytic, easily tunable synthetic approach for stereodivergent synthesis both E-selective and even more challenging Z-selective highly substituted 1,3-dienes from common substrates remains underexploited. Here, we report photoredox nickel dual catalytic strategy sulfonylalkenylation terminal alkynes with vinyl triflates sodium sulfinates under mild conditions. With judicious choice simple catalyst ligand, this method enables efficient divergent access to Z- E-sulfonyl-1,3-dienes same set starting materials. This features broad substrate scope, good functional compatibility, excellent chemo-, regio-, stereoselectivity. Experimental DFT mechanistic studies offer insights into observed stereoselectivity controlled by ligands.

Language: Английский

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Nickel(0)-catalyzed divergent reactions of silacyclobutanes with internal alkynes

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: June 13, 2022

Abstract Transition metal-catalyzed reactions of silacyclobutanes with a variety π units have attracted much attention and become one the most straightforward efficient approaches to rapidly access structurally diverse organosilicon compounds. However, reaction alkynes still suffers from some limitations: (1) internal remain challenging substrates; (2) expensive Pd- or Rh-based catalysts been employed in all existing systems; (3) controlling chemodivergence has not yet realized. Herein we realize Ni-catalyzed chemodivergent alkynes. In comparison previous Pd Rh catalytic systems, our Ni-catalytic system features: 1) complementary substrate scope; 2) ligand-controlled chemodivergence; 3) low cost. The ligand precisely dictates pathway selectivity, leading divergent formation (benzo)silacyclohexenes allyl vinylsilanes. Moreover, demonstrate that employment chiral phosphine is capable forming silicon-stereogenic vinylsilanes high yields enantioselectivities. addition, DFT calculation performed elucidate origin switchable selectivities, which mainly attributed different steric effects.

Language: Английский

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Endo-Selective Intramolecular Alkyne Hydroamidation Enabled by NiH Catalysis Incorporating Alkenylnickel Isomerization

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(22), P. 10064 - 10074

Published: May 27, 2022

Intramolecular alkyne hydroamidation represents a straightforward approach for the access to synthetically valuable cyclic enamides. Despite some advances made in this realm, ability attain precise regiocontrol still remains challenging, especially endo cyclization that leads six-membered and larger azacyclic rings. Herein, we report NiH-catalyzed intramolecular of alkynyl dioxazolones allows an excellent selectivity, thus affording range six- eight-membered endocyclic enamides with broad scope. Mechanistic investigations revealed Ni(I) catalysis is operative current system, proceeding via regioselective syn-hydronickelation, alkenylnickel E/Z isomerization, Ni-centered inner-sphere nitrenoid transfer. In particular, key isomerization step, which previously lacked mechanistic understandings, was found take place through η2-vinyl transition state. The synthetic value protocol demonstrated by diastereoselective modifications obtained highly functionalized δ-lactam scaffolds.

Language: Английский

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Recent Advances in the Functionalization of Terminal and Internal Alkynes

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(5)

Published: March 9, 2022

Abstract Alkynes are one of the most fundamental and diverse functional groups utilized in organic synthesis. Over past few years, development efficient synthetic methodologies for functionalization alkynes has been an active area research. A plethora alkyne reactions have reported literature to construct functionalized alkene scaffolds, which important building blocks many natural products, pharmaceuticals, key intermediates various transformations. In this review, we describe recent advances with emphasis on substrate scope, limitations, regioselectivity control applications these reactions. This review covers from 2016 2021.

Language: Английский

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Nickel‐Catalyzed Defluorinative Asymmetric Cyclization of Fluoroalkyl‐Substituted 1,6‐Enynes for the Synthesis of Seletracetam

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(46)

Published: Sept. 23, 2022

Abstract The introduction of fluorine‐containing groups into organic molecules can significantly affect their physical and chemical properties has long been used as an effective strategy for drug discovery development. Consequently, the development catalytic asymmetric methods synthesis heterocycles is highly desirable sought after. Herein, we describe a nickel‐catalyzed defluorinative cyclization fluoroalkyl‐substituted 1,6‐enynes, providing expedient access to synthetically attractive 4‐fluorovinyl‐substituted 2‐pyrrolidones in good yields with remarkable high levels chemo‐, regio‐, enantioselectivities (90–99 % ee,>35 examples). This protocol features readily available starting materials excellent functional group compatibility, exhibits complementary regioselectivity. utility this was demonstrated enantioselective antiepileptic Seletracetam.

Language: Английский

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Ni‐Catalyzed Divergent Synthesis of 2‐Benzazepine Derivatives via Tunable Cyclization and 1,4‐Acyl Transfer Triggered by Amide N‐C Bond Cleavage

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(25)

Published: April 6, 2022

Abstract Ligand‐directed divergent synthesis can transform common starting materials into distinct molecular scaffolds by simple tuning different ligands. This strategy enables the rapid construction of structurally rich collection small molecules for biological evaluation and reveals novel modes catalytic transformation, representing one most sought‐after challenges in synthetic chemistry. We herein report a Ni‐catalyzed ligand‐controlled tunable cyclization/cross‐couplings pharmacologically important 2‐benzazepine frameworks. The bidentate ligand facilitates nucleophilic addition aryl halides to amide carbonyl, followed 1,4‐acyl transfer cross‐coupling obtain 2‐benzazepin‐5‐ones benzo[c]pyrano[2,3‐e]azepines. tridentate promotes selective 7‐ endo cyclization/cross‐coupling access 2‐benzazepin‐3‐ones. protocol operates under mild reaction conditions with cyclization patterns that be easily modulated through backbone.

Language: Английский

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Enantioselective Metal-Catalyzed Reductive Coupling of Alkynes with Carbonyl Compounds and Imines: Convergent Construction of Allylic Alcohols and Amines

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(14), P. 8164 - 8174

Published: June 23, 2022

The use of alkynes as vinylmetal pronucleophiles in intermolecular enantioselective metal-catalyzed carbonyl and imine reductive couplings to form allylic alcohols amines is surveyed. Related hydrogen auto-transfer processes, wherein or serve dually reductants proelectrophiles, also are cataloged, applications target-oriented synthesis. These processes represent an emerging alternative the stoichiometric reagents Nozaki-Hiyama-Kishi (NHK) reactions alkenylation.

Language: Английский

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“Alkene-to-Alkene” Difunctionalization of Enaminones for the Synthesis of Polyfunctionalized Alkenes by Transition-Metal-Free C–H and C–N Bond Transformation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(47), P. 8451 - 8456

Published: Nov. 16, 2023

The three-component reactions of enaminones, disulfides, and alcohols for the synthesis polyfunctionalized alkenes have been realized via C-H C-N bond transformation on enaminones. proceed in a novel "alkene-to-alkene" difunctionalization mode without using any transition metal. application alkene products divergent sulfenyl heteroaryls, including sulfenylated pyrazoles, pyrimidines, isoxazoles, simple annulation has also verified.

Language: Английский

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