Cobalt-Catalyzed Acceptorless Dehydrogenation of Primary Amines to Nitriles

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(17), P. 11801 - 11810

Published: April 16, 2024

The direct double dehydrogenation from primary amines to nitriles without an oxidant or hydrogen acceptor is both intriguing and challenging. In this paper, we describe a non-noble metal catalyst capable of realizing such transformation with high efficiency. A cobalt-centered N,N-bidentate complex was designed employed as metal–ligand cooperative catalyst. Detailed kinetic studies, control experiments, DFT calculations revealed the crucial hydride transfer, proton evolution processes. Finally, tandem outer-sphere/inner-sphere mechanism proposed for through imine intermediate.

Language: Английский

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Single-Atom Fe-Catalyzed Acceptorless Dehydrogenative Coupling to Quinolines

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(33), P. 23338 - 23347

Published: Aug. 6, 2024

A single-atom iron catalyst was found to exhibit exceptional reactivity in acceptorless dehydrogenative coupling for quinoline synthesis, outperforming known homogeneous and nanocatalyst systems. Detailed characterizations, including aberration-corrected HAADF-STEM, XANES, EXAFS, jointly confirmed the presence of atomically dispersed centers. Various functionalized quinolines were efficiently synthesized from different amino alcohols a range ketones or alcohols. The achieved turnover number (TON) up 10

Language: Английский

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Selective C(sp3)-H bond Aerobic Oxidation Enabled by π-Conjugated Small Molecule-Oxygen Charge Transfer State

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(16), P. 9241 - 9249

Published: Jan. 1, 2024

A π-conjugated small molecule-oxygen charge transfer state enables selective C(sp 3 )–H oxidation, avoiding the use of photocatalysts, metals, and redox reagents.

Language: Английский

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Flow Electroreductive Nickel‐Catalyzed Cyclopropanation of Alkenes Using gem‐Dichloroalkanes

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 31, 2025

Abstract Cyclopropanes are valuable motifs in organic synthesis, widely featured pharmaceuticals and functional materials. Herein, we report an efficient electrochemical methodology for the cyclopropanation of alkenes, leveraging a nickel‐catalyzed process continuous‐flow. The developed protocol demonstrates broad substrate scope, accommodating both electron‐rich electron‐poor alkenes with high group tolerance. Beyond dichloromethane as feedstock methylene source, enables synthesis methylated, deuterated, chloro‐substituted cyclopropanes. Mechanistic investigations suggest electro‐generation nickel carbene key intermediate. Notably, reaction operates under ambient conditions, tolerates air moisture, achieves scalability through continuous‐flow technology, offering straightforward route to multi‐gram quantities enhanced throughput.

Language: Английский

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Catalytic remodeling of complex alkenes to oxonitriles through C=C double bond deconstruction

Science, Journal Year: 2025, Volume and Issue: 387(6738), P. 1083 - 1090

Published: March 6, 2025

Deconstructive transformation of carbon-carbon double bonds (C=C) is a pivotal strategy in synthetic chemistry and drug discovery. Despite the substantial advances olefin metathesis ozonolysis for natural product synthesis through C=C double-bond cleavage, catalytic remodeling complex molecules deconstruction has been underdeveloped. We report heterogeneous copper-catalyzed which enables by converting carbons on either side bond to carbonyl cyano groups, respectively. In particular, this method provides an efficient protocol conveniently transform terpenoids, glycals, steroids, bioactive privileged scaffolds with underexplored chemical space.

Language: Английский

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Bioinspired synthesis of cucurbalsaminones B and C

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

Published: Nov. 6, 2024

Cucurbalsaminones B (1) and C (2) are two abeo-cucurbitane triterpenoids with a unique 5/6/3/6/5-fused ring system exhibit potent multidrug resistance (MDR)-reversing activity. Herein, we report the first synthesis of these natural products, both them were accomplished in 14 steps from commercially available inexpensive resource compound lanosterol. Key features this include biomimetic tandem Wagner-Meerwein type lanostane-to-cucurbitane rearrangement followed by bioinspired photochemical oxa-di-π-methane (ODPM) to complete skeleton construction an Eosin Y photoinduced Barton-McCombie deoxygenation realize challenging oxidation state adjustment sterically hindered C11 position.

Language: Английский

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Metal-Free Electrochemical Allylic C–H Aerobic Oxidation

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 90(2), P. 1148 - 1158

Published: Jan. 8, 2025

A scalable and sustainable electrochemical protocol for allylic C–H aerobic oxidation has been developed, enabling the formation of enones without use stoichiometric toxic oxidants or metal catalysts offering an environmentally benign alternative to traditional chemical techniques. The process successfully applied selectively oxidize a series natural products drug molecules, underscoring its potential widespread adoption in both academic industrial contexts.

Language: Английский

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Palladium-catalyzed allylic C-H alkylation of terminal olefins with 3-carboxamide oxindoles

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A novel palladium-catalyzed allylic C-H alkylation of terminal olefins with 3-carboxamide oxindoles is described. variety new 3-carboxamide-3-allylation an all-carbon quaternary center were obtained in moderate to good yields (up 99%). In addition, the asymmetric version this reaction was also explored, providing enantioselectivity.

Language: Английский

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Biomass‐Derived Cu‐Catalyzed General C—X (X = C, N, O) Bond Formation: Carbenoid Insertion Reactions of C—H, N—H, O—H Bond and Late‐stage Functionalization of Drug Molecules^†

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 7, 2025

Comprehensive Summary The development of sustainable and efficient catalytic systems for the formation C—C, C—N, C—O bonds is a fundamental goal in modern synthetic chemistry. We present biomass‐derived Cu/Chitosan‐800 catalyst that facilitates range carbenoid insertion reactions into C—H, N—H, O—H bonds. This demonstrates remarkable activity, enabling functionalization diverse substrates, including late‐stage modification drug molecules with up to 95% yield good recyclability. Our findings highlight catalyst's potential advancing environmentally friendly chemical transformations, offering promising tool pharmaceutical synthesis organic synthesis.

Language: Английский

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Photo-induced aerobic deborohydroxylation of organoboron compounds in 1,3-dioxolane at room temperature

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 116006 - 116006

Published: Feb. 1, 2025

Language: Английский

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