Tetrahedron, Journal Year: 2024, Volume and Issue: 166, P. 134204 - 134204
Published: Aug. 17, 2024
Language: Английский
Nature, Journal Year: 2024, Volume and Issue: 628(8006), P. 104 - 109
Published: Feb. 13, 2024
Language: Английский
Citations
39
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(18), P. 12300 - 12309
Published: April 24, 2024
Metallaphotoredox cross-coupling is a well-established strategy for generating clinically privileged aliphatic scaffolds via single-electron reactivity. Correspondingly, expanding metallaphotoredox to encompass new C(
Language: Английский
Citations
20
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 9, 2025
The direct synthesis of C(sp3)-rich architectures is a driving force for innovation in synthetic organic chemistry. Such scaffolds impart beneficial properties onto drug molecules that correlate with greater clinical success. Consequently, there strong impetus to develop new methods by which access sp3-rich from commercial feedstocks, such as alkenes. Herein, we report three-component aminoalkylation reaction utilizes the principles triple radical sorting regioselectively add N-centered and C-centered radicals across This process relies upon photoredox catalysis transform alkyl bromides reductively activated precursors into high-energy species redox-neutral fashion. A broad scope coupling partners demonstrated, multiple applications, including facile syntheses pharmacophoric substituted N-heterocycles.
Language: Английский
Citations
3
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9404 - 9412
Published: March 20, 2024
The catalytic and enantioselective construction of quaternary (all-carbon substituents) stereocenters poses a formidable challenge in organic synthesis due to the hindrance caused by steric factors. One conceptually viable potentially versatile approach is coupling C–C bond through an outer-sphere mechanism, accompanied realization enantiocontrol cooperative catalysis; however, examples such processes are yet be identified. Herein, we present method for creating different compounds with photoredox/Fe/chiral primary amine triple catalysis. This facilitates connection unactivated alkyl source tertiary moiety, which also rare. scalable process exhibits mild conditions, does not necessitate use base, possesses good functional-group tolerance. Preliminary investigations into underlying mechanisms have provided valuable insights reaction pathway.
Language: Английский
Citations
13
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 11, 2025
A novel approach for the synthesis of pyrone and indanone derivatives utilizing Fe(III)-catalyzed reductive radical ring expansion olefins cyclopropenone has been proposed. The preliminary mechanism study shows that alkyl is formed by hydrogen atom transfer, which can open tension then generate intermediate. There are two paths intermediate: when there a hydroxyl group at β-position olefin, reaction produces pyrones, otherwise 1-indanone generated. This method mild conditions wide substrate adaptability allows fragment to be conveniently accessed.
Language: Английский
Citations
1
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
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
3
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
2
The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(22), P. 16106 - 16113
Published: June 26, 2024
This Synopsis covers recent reports of metal-catalyzed alkene functionalizations that likely involve iterative outer-sphere reactions in which the substrate reacts directly with a metal ligand instead center itself. Traditional hydride-catalyzed this latter pathway whereby forms part sphere (i.e. an inner-sphere reaction). In contrast, alkenes do not ligate so-called and react ligand. These transformations have proved crucial for synthesis high fraction sp3 (Fsp3) targets, especially hindered fragment couplings relevance to natural product space.
Language: Английский
Citations
1
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(41)
Published: July 10, 2024
Quaternary carbons are embedded in various natural products, pharmaceuticals, and organic materials. However, constructing this valuable motif is far from trivial. Conventional approaches mainly rely on classical polar disconnections encounter bottlenecks concerning harsh conditions, functional group tolerance, regioselectivity, step economy. In context, Kawamata, Baran, Shenvi, co-workers recently demonstrated that two feedstock chemicals, alkyl carboxylic acids olefins, could be utilized to construct tetrasubstituted the presence of an inexpensive iron porphyrin catalyst a suitable reductant combination through quaternization radical intermediates. The method enables access sterically encumbered quaternary under mild robust conditions. Taking complete detour conventional approaches, present heteroselective radical-radical coupling simplifies synthesis carbon-containing molecules innovative distinctive disconnection approach.
Language: Английский
Citations
1