Azobenzene-Integrated NHC Ligands: A Versatile Platform for Visible-Light-Switchable Metal Catalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(19), P. 13210 - 13225

Published: May 6, 2024

A new class of photoswitchable NHC ligands, named azImBA, has been developed by integrating azobenzene into a previously unreported imidazobenzoxazol-1-ylidene framework. These rigid photochromic carbenes enable precise control over confinement around metal's coordination sphere. As model system, gold(I) complexes these NHCs exhibit efficient bidirectional E–Z isomerization under visible light, offering versatile platform for reversibly photomodulating the reactivity organogold species. Comprehensive kinetic studies protodeauration reaction reveal rate differences up to 2 orders magnitude between E and Z isomers NHCs, resulting in quasi-complete visible-light-gated ON/OFF switchable system. Such high level photomodulation efficiency is unprecedented gold complexes, challenging current state-of-the-art organometallics. Thorough investigations ligand properties paired with structure–reactivity correlations underscored unique ligand's steric features as key factor reactivity. This effective photocontrol strategy was further validated catalysis, enabling situ photoswitching catalytic activity intramolecular hydroalkoxylation -amination alkynes. Given significance findings its potential widely applicable, easily customizable ancillary platform, azImBA poised stimulate development adaptive, multifunctional metal complexes.

Language: Английский

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Palladium-Catalyzed Dearomative para-/ortho-Cycloaddition Cascades of N-Allylanilines with 1,4-Enynes and CO via Skeletal Reorganization

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

A selectivity-control approach for palladium-catalyzed dearomative para-/ortho-cycloaddition cascades of aromatic compounds with 1,4-enynes and CO via a skeletal reorganization process to produce polycycle-fused bicyclo[2.2.2]octenes is reported. This mechanistically novel depends on that consists sequence [4 + 2] para-cycloaddition, 3,3-Cope rearrangement, carbon–carbon bond activation/[4 cycloaddition.

Language: Английский

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Green and rapid acid-catalyzed ynamide skeletal rearrangement and stereospecific functionalization with anisole derivatives

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(20), P. 8124 - 8133

Published: Jan. 1, 2023

Environmentally friendly acid-catalyzed 2-alkynyl-ynamides (N–Csp) bond cleavage, alkyne migration and stereospecific functionalization with anisole derivatives for the synthesis of challenging indole scaffolds in 5–10 minutes.

Language: Английский

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Five-membered ring systems: Furans and benzofurans

Progress in heterocyclic chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 175 - 209

Published: Jan. 1, 2024

Language: Английский

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Oxy-difluoroallylation of Ynamides by Nickel-Catalyzed Tandem Alkoxylation/Claisen Rearrangement

Organic Letters, Journal Year: 2024, Volume and Issue: 26(41), P. 8832 - 8836

Published: Oct. 9, 2024

A nickel-catalyzed tandem alkoxylation/claisen rearrangement strategy for the oxy-difluoroallylation of ynamides has been developed. In this reaction, 3,3-difluoroallyl alcohol was used as a fluorine-containing building block to construct C–CF2 bond first time. This approach is recognized its robust tolerance functional groups, impressive yields, and excellent atomic efficiency, all achieved under mild reaction conditions. series β,β-difluoromethyleneamide derivatives were efficiently obtained through simple operations, their practicality confirmed gram-scale synthesis product derivatization.

Language: Английский

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