Enabling Site-Selective C–H Functionalization of Aliphatic Alcohols and Amines with exo-Directing Groups by Tether-Tunable Design of Pd^II/Pd^IV Catalysis

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(22), P. 17077 - 17083

Published: Nov. 5, 2024

We report herein a general platform for palladium catalysis using library of cyclic diacyl peroxides, achieving site-selective C–H functionalization aliphatic alcohols and amines. Experimental studies theoretical calculations indicate that bystanding peroxides minimize unwanted reductive elimination events enable controlled cleavage. The protocol is simple scalable offers high selectivity broad range substrates nucleophiles, including complex molecules. findings advance understanding high-valent chemistry, providing tool creating chemically diverse vicinal diols amino opening new possibilities in functionalization.

Language: Английский

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A Unified Approach to Lactonization/Lactamization by Leveraging Tether-Tunable Distonic Radical Anions

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

Published: March 12, 2025

We report using visible-light-induced in situ generation of tether-tunable distonic radical anions for the general catalytic lactonization/lactamization aromatic carboxylic acids and benzamides. Its success relies on specific cyclic diacyl peroxide amount CsI, enabling electrophilic heteroatom-centered radicals via a philicity regulation strategy. Key features include operational simplicity, excellent functional group tolerance, broad substrate scope, high chemo- regioselectivity, gram-scale scalability, application to synthesis urolithin derivatives 3-n-butylphthalide.

Language: Английский

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Catalytic Fluorination of α-Branched Ketones with Nucleophilic Fluorine

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

Published: March 24, 2025

We herein disclose the first example of metal-free, redox-umpolung-enabled catalytic fluorination α-branched ketones with nucleophilic fluorine by judicious choice an oxidant. The strategic use cyclopropyl malonoyl peroxide in hypervalent iodine(III) catalysis expands modularity and generality construction α-fluorinated ideally orthogonal reactivity space, avoiding competing oxidation processes. Characteristic for this transformation is its operational simplicity, mild reaction conditions, gram-scale synthetic ability.

Language: Английский

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Intramolecular and intermolecular benzannulation of arylethanone derivatives enabled by visible light-induced catalytic generation of tether-tunable distonic radical anions

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A novel method enables inter-/intramolecular benzannulation to synthesize PAHs have been disclosed. Experimental and DFT data confirm the TDRA's role in HAA step of enolized 1,3-dicarbonyls via asynchronous PCET.

Language: Английский

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Advances in cellulose-based hydrogels: tunable swelling dynamics and their versatile real-time applications

RSC Advances, Journal Year: 2025, Volume and Issue: 15(15), P. 11688 - 11729

Published: Jan. 1, 2025

Cellulose-derived hydrogels have emerged as game-changing materials in biomedical research, offering an exceptional combination of water absorption capacity, mechanical resilience, and innate biocompatibility.

Language: Английский

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Photochemical Generation and Cycloadditions of Strained Cycloalkynes

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 20, 2025

Strained cycloalkynes and their utilization have enabled prospective tactical strategies for synthetic medicinal chemistry, chemical biology, materials science, allied fields. However, full potential remains largely underexplored due to the limited availability of efficient sp3-rich cycloalkyne precursors with high efficiency structural complexity. Herein, we describe an intuitive modular photochemical approach liberate analogs from cyclic diacyl peroxides, without external reagents. This disclosed platform hinges on leverage realize two distinct classes strain-promoted cycloadditions straightforward construction diverse polycyclic scaffolds production any side product except nitrogen CO2. Moreover, functional group tolerance, biorelevant molecules compatibility, scalability, late-stage functionalization bioactive demonstrate utility presented methods. These features enrich assembling cycloalkenyl-containing diversity, offering new opportunities click chemistry bioorthogonal reactions.

Language: Английский

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Photoinduced cross-coupling of aryl halides enabled by n-tetrabutylphosphonium phthalate

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(23), P. 6718 - 6727

Published: Jan. 1, 2024

Phthalate acts as an electron shuttle bridge to realize aryl cross-coupling reactions by two-point non-covalent interaction.

Language: Английский

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Manganese‐ Mediated Cascade Radical Oxidative Cyclization/1,6‐Conjugate Addition of Unsaturated Oximes with p‐Quinone methides: Facile Access to β,β‐Diarylmethine Isoxazolines

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 9, 2024

A simple and efficient strategy for the synthesis of structurally diverse β,β-diarylmethine substituted isoxazoline derivatives have been developed. This approach employs a manganese-promoted oxidative cyclization coupled with 1,6-conjugate addition unsaturated oximes to p-quinone methides. The key features this study include formation C-O C-C bonds through intramolecular intermolecular interactions, facilitated by in situ generated iminoxyl radicals. isoxazolines, bearing wide range functional groups, were isolated high yields.

Language: Английский

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