Photoredox/Nickel Dual Catalysis-Enabled Modular Synthesis of Arylallyl Alcohols with Acetylene as the Two-Carbon Synthon

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2422 - 2431

Published: Feb. 2, 2023

Arylallyl alcohols are commonly found in natural products and drug molecules. The traditional syntheses primarily rely on two-component reactions using presynthesized alkenes. Herein, we report a photoredox/nickel dual-catalyzed three-component cross-coupling reaction, which enables the rapid synthesis of arylallyl with acetylene as two-carbon (C2) synthon. In this aryl halide carbonyl compound were sewn together linker. A series synthesized an atmosphere (1 atm). This method features broad substrate scopes, good functional group tolerance, high Z-selectivity. addition to intermolecular difunctionalization acetylene, reaction is also amenable intramolecular ring formation, giving highly valuable indenols indanones. mechanistic investigation indicates that alkenylnickel key intermediate. intermediate can be considered alternative alkenyl Grignard reagent but better compatibility. With step, several important molecules including have been prepared.

Language: Английский

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Calcium carbide: Highly potent solid reagent for the construction of heterocycles

Tetrahedron, Journal Year: 2023, Volume and Issue: 149, P. 133720 - 133720

Published: Nov. 1, 2023

Language: Английский

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Construction of 3-Methyl-2-Substituted Benzo[b]furans and 3-Methyl-2-Substituted Benzo[b]thiophenes Using Solid Calcium Carbide as a Substitute for Gaseous Acetylene

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(10), P. 7182 - 7186

Published: May 2, 2024

A concise method for the facile construction of 3-methyl-2-substituted benzo[b]furans and benzo[b]thiophenes using low-cost, abundant, easy-to-use solid calcium carbide instead flammable explosive gaseous acetylene as an original alkyne source, o-bromophenyl ethers or thioethers substrates through intramolecular carbanion-yne cyclization in a 5-exo-dig manner, subsequent double-bond isomerization is described. The simultaneous formation two C–C bonds realized one-step route. wide substrate scope, high yield, simple workup manipulations are also merits this method. synthetic strategy can be suitable gram scale.

Language: Английский

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Bifunctional two-carbon reagent made from acetylene via 1,2-difunctionalization and its applications

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(3), P. 936 - 944

Published: Jan. 8, 2024

Language: Английский

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Recent progress in the catalytic transformation of acetylene

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Acetylene, a traditional industrial raw material, has garnered increasing attention in modern organic synthesis over the past two decades.

Language: Английский

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Gold(I)-Catalyzed Intermolecular Aryloxyvinylation with Acetylene Gas

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(16), P. 10751 - 10755

Published: Aug. 1, 2023

Acetylene gas is an important feedstock for chemical production, although it underutilized in organic synthesis. We have developed intermolecular gold(I)-catalyzed alkyne/alkene reaction of o-allylphenols with acetylene that gives rise to chromanes by a stereospecific aryloxycyclization through the nucleophilic regioselective opening cyclopropyl gold(I)-carbene intermediates. The synthetic application this method was demonstrated late-stage functionalization natural product lapachol.

Language: Английский

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Photoinduced synthesis of C2-linked phosphine oxides via radical difunctionalization of acetylene

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(18), P. 7253 - 7258

Published: Jan. 1, 2023

A photocatalyzed radical difunctionalization of acetylene was achieved, which enables the green synthesis C2-linked phosphine oxides.

Language: Английский

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Ligand Control of Copper-Mediated Cycloadditions of Acetylene to Azides: Chemo- and Regio-Selective Formation of Deutero- and Iodo-Substituted 1,2,3-Triazoles

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 89(2), P. 825 - 834

Published: Dec. 28, 2023

The participation of σ-monocopper and σ-bis-copper acetylide in mechanistic pathways for copper-catalyzed cycloaddition (CuAAC) reactions acetylene with azides was probed by analysis deuterium distributions the 1,2,3-triazole product formed deuterolysis initially mono- bis-copper triazoles. results show that, when Cu(Phen)(PPh3)2NO3 is used as catalyst DMF/D2O, 1-substituted-5-deutero-1,2,3-triazoles are generated selectively. This finding demonstrates that Cu(Phen)(PPh3)2NO3-catalyzed cycloadditions utilize monocopper substrate produce 5-copper-1,2,3-triazoles initially. Conversely, DBU or Et3N copper ligand, process takes place through initial formation to 4,5-bis-copper-triazole, which reacts D2O form corresponding 4,5-bis-deutero-triazole. Moreover, C2D2 substrate, Cu H2O/DMF solvent, mono-C4-deutreo 1,2,3-triazoles high yields excellent levels regioselectivity. Lastly, CuAAC azides, promoted CuCl2·2H2O NaI, yield 4,5-diiodo-1,2,3-triazoles moderate efficiencies.

Language: Английский

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Modular and Diverse Synthesis of Acrylamides by Palladium‐Catalyzed Hydroaminocarbonylation of Acetylene

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 10, 2024

The development of all kinds covalent drugs had a major impact on the improvement human health system. Covalent binding to target proteins is achieved by so-called electrophilic warheads, which are incorporated in respective drug molecule. In last decade, specifically acrylamides emerged as attractive warheads design. Herein, straightforward palladium-catalyzed hydroaminocarbonylation acetylene has been developed, allowing modular and diverse synthesis bio-active acrylamides. This general protocol features high atom efficiency, wide functional group compatibility, chemoselectivity proceeds additive free under mild reaction conditions. synthetic utility this showcased ibrutinib, osimertinib, other compound derivatives.

Language: Английский

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Modular and Diverse Synthesis of Acrylamides by Palladium‐Catalyzed Hydroaminocarbonylation of Acetylene

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(40)

Published: July 10, 2024

Abstract The development of all kinds covalent drugs had a major impact on the improvement human health system. Covalent binding to target proteins is achieved by so‐called electrophilic warheads, which are incorporated in respective drug molecule. In last decade, specifically acrylamides emerged as attractive warheads design. Herein, straightforward palladium‐catalyzed hydroaminocarbonylation acetylene has been developed, allowing modular and diverse synthesis bio‐active acrylamides. This general protocol features high atom efficiency, wide functional group compatibility, chemoselectivity proceeds additive free under mild reaction conditions. synthetic utility this showcased ibrutinib, osimertinib, other compound derivatives.

Language: Английский

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