Dual Relay Rh-/Pd-Catalysis Enables β-C(sp3)-H Arylation of α-Substituted Amines

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A dual relay catalytic protocol, built on reversible dehydrogenation of amines by Rh catalysis and C-H functionalisation transient imines Pd catalysis, is reported to enable regioselective arylation at their unactivated β-C(sp3)-H bond. Notably, the new strategy applicable secondary anilines N-PMP-protected primary aliphatic intermediate steric demands, which in contrast existing strategies that involve either free-amine-directed activation for highly sterically hindered or steric-controlled migrative cross-coupling unhindered N-Boc protected amines. Regioselectivity reaction imposed electronic effects imine intermediates rather than between specific starting materials catalysts, thereby opening uncharted scope In a broader sense, this study demonstrates opportunities involving hydrogen borrowing chemistry, previously explored alcohols, execute otherwise challenging transformations amines, commonly present natural products, pharmaceuticals, biologically active molecules, functional materials.

Language: Английский

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Selectivity Effects of Hydrogen Acceptors and Catalyst Structures in Alcohol Oxidations Using (Cyclopentadienone)iron Tricarbonyl Compounds

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 90(5), P. 2036 - 2051

Published: Jan. 23, 2025

Oppenauer-type oxidations are catalyzed by air- and moisture-stable, sustainable, (cyclopentadienone)iron carbonyl compounds, but the substrate scope is limited due to low reduction potential of acetone, which most commonly used hydrogen acceptor. We discovered that furfural, an aldehyde derived from cellulosic biomass, effective acceptor with this class catalysts. In general, reactions using furfural as led higher isolated yields ketones aldehydes compared those acetone. Importantly, primary benzylic allylic alcohols─typically a challenging alcohols oxidize these catalysts─could be oxidized. The selectivity for vs secondary alcohol oxidation catalysts was also explored acetone acceptors. Most tested preferentially oxidized unhindered alcohols, trialkylsilyl groups in 2- 5-positions cyclopentadienone alcohols. A combination experiments kinetic studies concluded trialkylsilyl-based kinetically derived─primary were more quickly than secondary─and other arose equilibrium-driven nature oxidation.

Language: Английский

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Shining a light on Fe-catalyzed borrowing hydrogen alkylation

Trends in Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 1, 2025

Language: Английский

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Construction of effective and recyclable non-precious metal coordination polymers and their multiple applications in water

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111165 - 111165

Published: April 1, 2025

Language: Английский

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Enantioselective [5 + 1] cycloaddition of sulfur ylides and vinylethylene carbonates via synergistic palladium/chiral phosphonic acid catalysis

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

An effective method for the synthesis of dihydropyrans through synergistic palladium and chiral phosphonic acid catalysis was reported. This protocol proceeded under mild reactions provided in up to 87% yield 97% ee.

Language: Английский

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Deoxygenative 1,3-Carbophosphination of Allylic Alcohols enabled by Manganese Pincer Catalyst

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

The first manganese-catalyzed three-component coupling between secondary alcohol, allylic and phosphine via borrowing hydrogen is described. This four-stage, one-pot reaction afforded ε-hydroxy phosphines in a step-economical fashion.

Language: Английский

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