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This study reports selective dual amino acylation and C-H bromination of aniline compounds enabled by Cu/O2 catalyst systems. This method involves crucial oxidation-induced C-CN bond cleavage of α-methylene nitriles to generate an acylcyanide intermediate that is facilely intercepted by anilines. After amino acylation, the Cu(II) precatalyst in combination with NBS generates Cu(III)-Br in situ that engages in selective electrophilic para- or ortho-C-H bromination. The substrate scope, mechanistic aspects, and late-stage functionalization of biologically active anilines are studied. This study shows the synthetic potential of oxidative C-CN bond activation of nitriles for the development of valuable reactions.
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C-Alkyl glycosides, an important class of C-glycosides, are widely found in various drugs and natural products. The synthesis of C-alkyl glycosides has attracted considerable attention. Herein, we developed a Ni/photoredox catalyzed decarboxylative C(sp3)-C(sp3) coupling reaction of stable glycosylcarboxylic acids with simple aliphatic bromides to generate C-alkyl glycosides. The method successfully linked several functional molecular fragments (natural products or drugs) to a sugar moiety, showing the extensive application prospects of this transformation. Controlled experiments and DFT calculations demonstrated that the reaction pathway contains a free radical process, and a possible mechanism is proposed.
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C-aryl glycosides are popular basic skeletons in biochemistry and pharmaceutical chemistry. Herein, ruthenium-catalyzed highly stereo- and site-selective ortho- and meta-CAr -H glycosylation is described. A series of C-aryl pyranosides and furanosides were synthesized by this method. The strategy showed good substrate scope, and various N-heterocyclic directing groups were compatible with the reaction system. A mechanistic study suggested that the key pathway of ortho-CAr -H glycosylation might involve oxidative addition/reduction elimination, whereas aryl meta-C-H glycosylation was mediated by σ-activation. Density functional theory calculations also showed that the high stereoselectivity of meta-CAr -H glycosylation was due to steric hindrance.
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Rutênio , Catálise , Glicosilação , OxirreduçãoRESUMO
Copper-catalyzed three-component redox-neutral ring opening of benzothiazoles with aryl iodides and O-benzoyl hydroxylamines for the synthesis of 1-amino-N-(2-(phenylthio)phenyl)methanimine has been developed. This one-pot reaction undergoes C-S and N-O bond cleavage and new C-S and C-N bond construction. Several control experiments excluded a free radical procedure and also demonstrated the secondary amine as a possible intermediate, which was vital to the catalytic reaction. Meanwhile, the deuteration experiment got rid of the C-H activation dehydroisomerization of the benzothiazole mechanism.
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This report describes the first example of palladium-catalyzed ortho-C-H glycosylation/ipso-alkenylation of aryl iodides, and the easily accessible glycosyl chlorides are used as a glycosylation reagent. The reaction is compatible with the functional groups of the substrates, and a series of C-aryl glycosides have been synthesized in good to excellent yield and with excellent diastereoselectivity. It is found that a cheap 5-norbornene-2-carbonitrile as a transient mediator can effectively promote this reaction. In addition, ipso-arylation and cyanation were also realized by the strategy.
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Herein, we present a novel Catellani-type reaction that employed aryl-thianthrenium salts as aryl substrates to trigger the subsequent palladium/norbornene cooperatively catalyzed progress. This strategy can achieve site-selective C-H difunctionalization of aryl compounds without directing groups or a known initiating reagent. A series of functionalized syntheses of bioactive molecules further demonstrated the potential of this strategy.
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With in-depth research on 1,2-difunctionalization, remote difunctionalization has garnered widespread attention for achieving multifunctionality. Herein, we report a strategy for achieving remote difunctionalization under mild conditions. This strategy exhibited good substrate suitability and functional group tolerance. In addition, the significance of this method is further evidenced by its successful application in scaling up and conducting additional transformations of target compounds. Mechanistic studies showed that a radical might be involved in this process.
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To investigate the significance of atherosclerotic plaque location in hybrid surgery comprising both endovascular recanalization approaches and carotid endarterectomy for symptomatic atherosclerotic non-acute long-segment occlusion of the internal carotid artery (ICA), 162 patients were enrolled, including 120 (74.1%) patients in the proximal plaque group and 42 (25.9%) in the distal plaque group. Surgical recanalization was performed in all patients, with successful recanalization in 119 (99.2%) patients in the proximal and 39 (92.9%) in the distal plaque group. The total successful recanalization rate was 97.5% (158/162) with a failure rate of 2.5% (4/162). Periprocedural complications occurred in 5 (4.2% or 5/120) patients in the proximal plaque group, including neck infection in two (1.7%), recurrent nerve injury in 1 (0.8%), and laryngeal edema in 2 (1.7%), and 2 (4.8%) in the distal plaque group, including femoral puncture infection in 2 (4.8%). No severe complications occurred in either group. Univariate analysis showed plaque location was a significant (P = 0.018) risk factor for successful recanalization, and multivariate analysis indicated that the plaque location remained a significant independent risk factor for recanalization success (P = 0.017). In follow-up 6-48 months after the recanalization surgery, reocclusion occurred in two (2.8%) patients in the proximal plaque group and 4 (13.3%) in the distal plaque group. In conclusion, although hybrid surgery achieves similar outcomes in patients with ICA occlusion caused by either proximal or distal atherosclerotic plaques, plaque location may be a significant risk factor for successful recanalization of symptomatic non-acute long-segment ICA occlusion.
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Artéria Carótida Interna , Estenose das Carótidas , Endarterectomia das Carótidas , Placa Aterosclerótica , Humanos , Masculino , Feminino , Idoso , Placa Aterosclerótica/cirurgia , Placa Aterosclerótica/patologia , Placa Aterosclerótica/complicações , Artéria Carótida Interna/cirurgia , Artéria Carótida Interna/patologia , Pessoa de Meia-Idade , Estenose das Carótidas/cirurgia , Estenose das Carótidas/patologia , Estenose das Carótidas/complicações , Endarterectomia das Carótidas/métodos , Resultado do Tratamento , Procedimentos Endovasculares/métodos , Idoso de 80 Anos ou mais , Fatores de RiscoRESUMO
We report a redox-neutral, visible-light-mediated difluoroalkylation of unactivated C(sp3)-H bonds in amides via nitrogen-centered radicals triggered intramolecular hydrogen atom transfer. Notably, all types (tertiary, secondary, and primary) of γ-C(sp3)-H bonds displayed excellent reactivity. This methodology presents a facile route for the regioselective introduction of α,α-difluoroketone fragments into organic molecules. Moreover, the resulting gem-difluoroketones can be readily converted to structurally diverse difluoro-containing molecules, offering broad potential applications in medicinal chemistry and chemical biology.
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Amidas , Hidrogênio , Amidas/química , Catálise , Hidrogênio/química , Nitrogênio/química , Oxirredução , AlquilaçãoRESUMO
Polysubstituted alkenes are an important class of organic intermediates that widely exist in various natural products and drug molecules. Herein, we reported a stereoselective synthesis of multisubstituted alkenes via ruthenium-catalyzed remote migration arylation of nonactivated olefins. This strategy exhibited wide substrate suitability and excellent functional group tolerance. In addition, we demonstrated the indispensable role of two types of ruthenium through mechanism experiments.
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Alcenos , Rutênio , Alcenos/química , Rutênio/química , Catálise , EstereoisomerismoRESUMO
A visible-light-induced glycoarylation of activated olefins has been accomplished. Glycosyl radicals are generated via radical transfer strategies between (TMS)3SiOH and glycosyl bromides. Subsequent radical translocation and rapid 1,4-aryl migration form ß-sugar amide derivatives, and eight types of sugars are compatible with this reaction. Further, the cascade reaction produced a quaternary carbon center with good functional group adaptability and high regioselectivity in mild conditions.
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This manuscript describes an unusual Pd-catalyzed rearrangement reaction. It provides efficient access to 1-phenanthrol derivatives using allyloxy-tethered aryl iodides. This rearrangement process involves the cleavage of a C-I bond, a C-O bond and C-H bonds, and the formation of two C-C bonds in one-pot. It is likely that the key to the success of this rearrangement is via ß-carbon elimination from a strained palladacycle.
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Herein, we realized the multicomponent reactions of phenol derivatives via a six-membered cycloruthenated intermediate for the first time. This strategy exhibited good substrate suitability and functional group tolerance with various phenol derivatives and provided a potential synthetic drug approach. Mechanistic studies showed that a radical might be involved in this process. In addition, the meta alkylated phenol was obtained by further removal of the directing group.
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Construction of C(sp2)-C(sp3) bonds via regioselective coupling of C(sp2)-H/C(sp3)-H bonds is challenging due to the low reactivity and regioselectivity of C-H bonds. Here, a novel photoinduced Ru/photocatalyst-cocatalyzed regioselective cross-dehydrogenative coupling of dual remote C-H bonds, including inert γ-C(sp3)-H bonds in amides and meta-C(sp2)-H bonds in arenes, to construct meta-alkylated arenes has been accomplished. This metallaphotoredox-enabled site-selective coupling between remote inert C(sp3)-H bonds and meta-C(sp2)-H bonds is characterized by its unique site-selectivity, redox-neutral conditions, broad substrate scope and wide use of late-stage functionalization of bioactive molecules. Moreover, this reaction represents a novel case of regioselective cross-dehydrogenative coupling of unactivated alkanes and arenes via a new catalytic process and provides a new strategy for meta-functionalized arenes under mild reaction conditions. Density functional theory (DFT) calculations and control experiments explained the site-selectivity and the detailed mechanism of this reaction.
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Herein, we describe the copper-catalyzed arylalkylation of activated alkenes via hydrogen-atom transfer and aryl migration strategy. The reaction was carried out through a radical-mediated continuous migration pathway using N-fluorosulfonamides as the alkyl source. The primary, secondary, and tertiary alkyl radicals formed by intramolecular hydrogen-atom transfer proceeded smoothly. This methodology is an efficient approach for the synthesis of various amide derivatives possessing a quaternary carbon center with good yields and high regioselectivity.
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We described a novel palladium-catalyzed C-H glycosylation of indole or tryptophan for a one-pot stereoselective synthesis of 2,3-diglycosylindoles and tryptophan-C-glycosides. In this strategy, the use of air and base-free and ligand-free conditions provided a highly efficient route to construct C-glycosides. The method can be applied to a wide range of cost-effective and convenient glycosyl chloride donors. Mechanistic studies indicated that the indole 2,3-diglycosylation sequence was C3 and then C2.
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Paládio , Triptofano , Catálise , Glicosídeos , Glicosilação , IndóisRESUMO
This Letter describes a Pd-catalyzed Tsuji-Trost-type/Heck reaction with allyloxy-tethered aryl iodides and aziridines. The strategy provides efficient access to benzannulated medium-sized rings via intermolecular cyclization. The substrate aryl iodide has two oxidative addition sites, that is, the aromatic C-I bond and the allyl-oxygen bond. The chemoselective oxidative addition of allyl-oxygen bonds is favored, followed by the activation of aromatic C-I bonds. Aziridine plays a key role. Mechanistic studies shed light on the reaction pathway.
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We developed a new transition-metal-free intermolecular Claisen rearrangement process to introduce allyl and allenyl groups into the α position of tertiary amides. In this transformation, amides were activated by trifluoromethanesulfonic anhydride to produce the keteniminium ion intermediates that exhibit strong electrophilic activity. This atom-economical process delivers α position-modified amides under mild conditions in moderate to good yields and showcases a broad substrate compatibility.
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We described a novel palladium-catalyzed domino procedure for the preparation of (hetero)aryl thio/selenoglycosides. Readily available (hetero)aryl iodides and easily accessible 1-thiosugars/1-selenosugars are utilized as the substrates. Meanwhile, 10 types of sugars are quite compatible with this reaction with good regio- and stereoselectivity, high efficiency, and broad applicability (up to 89%, 53 examples). This method enables the straightforward formation of the C(sp2)-S/Se bond of (hetero)aryl thio/selenoglycosides.
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Iodetos/química , Compostos Organosselênicos/síntese química , Catálise , Estrutura Molecular , Compostos Organosselênicos/química , Paládio/químicaRESUMO
C-Aryl glycosides are of high value as drug candidates. Here a novel and cost-effective nickel catalyzed ortho-CAr-H glycosylation reaction with high regioselectivity and excellent α-selectivity is described. This method shows great functional group compatibility with various glycosides, showing its synthetic potential. Mechanistic studies indicate that C-H activation could be the rate-determining step.