Green Synthesis and Catalysis, Journal Year: 2024, Volume and Issue: unknown
Published: Sept. 1, 2024
Language: Английский
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(35)
Published: June 7, 2024
We report a photochemical method for the semipinacol rearrangement of unactivated allylic alcohols. Aliphatic as well aromatic groups participate migrating groups, yielding variety α,α-disubstituted ketones. The reaction proceeds under mild conditions and is compatible with ethers, esters, halides, nitriles, carbamates, substituted arenes. operationally simple fully catalytic prescribe 1 mol % benzothiazinoquinoxaline organophotocatalyst, 0.5 Co-salen, 10 lutidinium triflate and, importantly, display reactivity complementary to procedures employing Brønsted acid. showcase utility protocol in late-stage drug diversifications.
Language: Английский
Citations
9
Chemical Science, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 1, 2025
An applicable cobalt-hydride-mediated selective, divergent hydroetherification and sequential hydroetherification/hydroarylation of 1,3-dienes with simple phenol feedstocks under a photoredox cobalt catalytic system have been developed. A variety allyl aryl ethers value-added chroman derivatives can be obtained in good to excellent yields stereoselectivity. This method not only obviates the need for extra hydrosilanes stoichiometric oxidants, thereby offering exceedingly mild conditions alkene hydroetherification, but also represents first case CoH-HAT-catalyzed double hydrofunctionalization alkenes sole nucleophile. The continuous selective bond-forming expands applications cobalt-hydride MHAT reaction provides novel approach design synthesis heterocyclic molecules.
Language: Английский
Citations
1
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: Aug. 22, 2024
Abstract We herein report radical hydroazidation and hydrohalogenation of mono-, di- trisubstituted alkenes through iron catalysis. The alkene moiety that often occurs as a functionality in natural products is readily transformed into useful building blocks this approach. Commercially available tosylates α-halogenated esters are used trapping reagents combination with silanes reductants. reported Markovnikov hydroazidation, hydrobromination, hydrochlorination, hydroiodination occur under mild conditions. These hydrofunctionalizations valuable practical alternatives to ionic hydrohalogenations the corresponding mineral acids have be run harsher acidic conditions, which diminishes functional group tolerance. Good excellent diastereoselectivities can obtained for hydrofunctionalization cyclic alkenes.
Language: Английский
Citations
5
Bulletin of the Korean Chemical Society, Journal Year: 2024, Volume and Issue: 45(9), P. 738 - 758
Published: Sept. 1, 2024
Abstract Halogenation is one of the most important transformations in organic synthesis. Halogenated compounds are employed many reactions to prepare useful molecules. Many methods have been developed introduce halogens into different compounds. Visible light‐mediated efficient, low‐toxic, and mild‐condition applied for various chemistry transformations. Remarkably, there has an increasing development application visible light‐induced halogenation recent years. Herein, we present a comprehensive summary including chlorination, bromination, iodination under light irradiation since 2020.
Language: Английский
Citations
5
ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(10), P. 8005 - 8012
Published: May 9, 2024
We report intra- and intermolecular γ-amino C(sp3)–H functionalization of aliphatic amines using a vinylsulfone-based HAT (hydrogen atom transfer) auxiliary triple catalysis, which is composed photoredox, cobalt, Brønsted acid catalysts under visible light irradiation. The process accomplishes four elementary steps: (i) electrophilic carbon-centered radical formation on the via MHAT (metal hydride hydrogen reaction, (ii) generation through 1,6-HAT (iii) single-electron oxidation to carbocation equivalents, (iv) nucleophilic substitution with internal or external nucleophiles. As result, this afforded γ-amino-functionalized products, such as azetidines, 1,3-diamine, 1,3-aminoalcohol derivatives.
Language: Английский
Citations
4
Chem, Journal Year: 2024, Volume and Issue: 10(10), P. 3088 - 3099
Published: June 19, 2024
Language: Английский
Citations
4
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: July 16, 2024
Current methodologies for the functionalization of [1.1.1]propellane primarily focus on achieving 1, 3-difunctionalized bicyclo[1.1.1]pentane or ring-opened cyclobutane moiety. Herein, we report an innovative approach 3-difunctionalization [1.1.1]propellane, enabling access to a diverse range highly functionalized cyclobutanes via nucleophilic attack followed by ring opening and iron-hydride hydrogen atom transfer. To enable this method, developed efficient iron-catalyzed hydropyridylation various alkenes C - H alkylation pyridines at C4 position, eliminating need stoichiometric quantities oxidants reductants. Mechanistic investigations reveal that resulting N-centered radical serves as effective oxidizing agent, facilitating single-electron transfer oxidation reduced iron catalyst. This process efficiently sustains catalytic cycle, offering significant advantages substrates with oxidatively sensitive functionalities are generally incompatible alternative approaches. The strategy presented herein is not only mechanistically compelling but also demonstrates broad versatility, highlighting its potential late-stage functionalization.
Language: Английский
Citations
4
Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14865 - 14871
Published: Jan. 1, 2024
A novel photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated alkenes with aryl bromides by using proton as a hydrogen source has been developed for the first time.
Language: Английский
Citations
4
Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: Aug. 13, 2024
Persistent radicals facilitate numerous selective radical coupling reactions. Here, we have identified acyl triazole as a new and versatile moiety for generating persistent intermediates through single-electron transfer processes. The efficient generation of these is facilitated by the formation substrate-coordinated cobalt complexes, which subsequently engage in cross-coupling Remarkably, triazole-coordinated complexes exhibit metal-hydride hydrogen atom (MHAT) capabilities with alkenes, enabling synthesis diverse ketone products without need external ligands. By leveraging effect, this catalytic approach also allows development other reactions two representative precursors. discovery triazoles effective substrates ligands catalysis, combined bifunctional nature system, opens up avenues design sustainable organic transformations. radical-mediated has emerged powerful tool forging C–C bonds. authors identify processes, context cobalt-catalysed carbon-carbon couplings under photoirradiation.
Language: Английский
Citations
4
Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 4893 - 4897
Published: June 5, 2024
Cobalt-catalyzed metal hydride hydrogen atom transfer (MHAT) in combination with photoredox catalysis has emerged as a powerful synthetic method, owing to its redox nature and applicability various radical precursors. Herein, we describe cross-radical coupling reaction under cobalt/photoredox dual catalysis. MHAT homolytic substitution (SH2) processes enabled Markovnikov-selective hydrobenzylation of di/trisubstituted alkenes, affording products quaternary carbon center redox-neutral manner.
Language: Английский
Citations
3