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Upstream product

• 91-22-5 quinoline 
• 98546-51-1 (4-thiomethoxyphenyl)boronic acid 
• 2005-43-8 2-bromoquinoline 
• 271-58-9 anthranil 
• 134317-21-8 1-methylthio-4-[2-(trimethylsilyl)ethynyl]benzene 
• 5344-90-1 2-Aminobenzyl alcohol 
• 32293-73-5 α-methyl-4-(methylthio)benzenemethanol 
• 1778-09-2 4-(Methylthio)acetophenone 
• 612-25-9 2-Nitrobenzyl alcohol 
• 612-62-4 2-Chloroquinoline 

Relevant academic research and scientific papers

Catalytic Aerobic Dehydrogenation of Nitrogen Heterocycles Using Heterogeneous Cobalt Oxide Supported on Nitrogen-Doped Carbon

Dehydrogenation of (partially) saturated heterocycles provides an important route to heteroaromatic compounds. A heterogeneous cobalt oxide catalyst, previously employed for aerobic oxidation of alcohols and amines, is shown to be effective for aerobic dehydrogenation of various 1,2,3,4-tetrahydroquinolines to the corresponding quinolines. The reactions proceed in good yields under mild conditions. Other N-heterocycles are also successfully oxidized to their aromatic counterparts.

Modular Access to Spiro-dihydroquinolines via Scandium-Catalyzed Dearomative Annulation of Quinolines with Alkynes

The catalytic enantioselective construction of three-dimensional molecular architectures from planar aromatics such as quinolines is of great interest and importance from the viewpoint of both organic synthesis and drug discovery, but there still exist many challenges. Here, we report the scandium-catalyzed asymmetric dearomative spiro-annulation of quinolines with alkynes. This protocol offers an efficient and selective route for the synthesis of spiro-dihydroquinoline derivatives containing a quaternary carbon stereocenter with an unprotected N-H group from readily accessible quinolines and diverse alkynes, featuring high yields, high enantioselectivity, 100% atom-efficiency, and broad substrate scope. Experimental and density functional theory studies revealed that the reaction proceeded through the C-H activation of the 2-aryl substituent in a quinoline substrate by a scandium alkyl (or amido) species followed by alkyne insertion into the Sc-aryl bond and the subsequent dearomative 1,2-addition of the resulting scandium alkenyl species to the C=N unit in the quinoline moiety. This work opens a new avenue for the dearomatization of quinolines, leading to efficient and selective construction of spiro molecular architectures that were previously difficult to access by other means.

NiH-Catalyzed Hydroamination/Cyclization Cascade: Rapid Access to Quinolines

Despite the significant success of metal-H-catalyzed hydroamination methodologies, considerable limitations still exist in the selective hydroamination of alkynes, especially for terminal alkynes. Herein, we develop a highly efficient NiH catalytic system that activates readily available alkynes for a cascade hydroamination/cyclization reaction with anthranils. This mild, operationally simple protocol is amenable to a wide array of alkynes including terminal and internal, aryl and alkyl, electron-deficient and electron-rich ones, delivering structurally diverse quinolines in useful to excellent yields (>80 examples, up to 93% yield). The utility of this procedure is exhibited in the late-stage functionalization of several natural products and in the concise synthesis of an antitumor molecule graveolinine and a triplex DNA intercalator. Preliminary mechanistic experiments suggest an alkenylnickel-mediated alkyne hydroamination and an intramolecular cyclization/aromatization of putative enamine intermediates.

Organometal-Free Arylation and Arylation/Trifluoroacetylation of Quinolines by Their Reaction with CF3-ynones and Base-Induced Rearrangement

The reaction of quinolines with CF3-ynones resulted in the formation of 1,3-oxazinoquinolines. Subsequent treatment of the reaction mixture with a base initiated deep structural transformation of primary products. Both steps proceed in very high yield. As a result, unusual rearrangement of 1,3-oxazinoquinolines to form either 2-arylquinolines or 2-aryl-3-trifluoroacetylquinolines was discovered. The decisive role of the base in the reaction direction was shown. Using these reactions, highly efficient pathways to 2-arylquinolines and 2-aryl-3-trifluoroacetylquinolines were elaborated to provide the corresponding compounds in high yields using a simple one-pot procedure. The possible mechanism of rearrangement is discussed.

Homogeneous Nickel-Catalyzed Sustainable Synthesis of Quinoline and Quinoxaline under Aerobic Conditions

Dehydrogenative coupling-based reactions have emerged as an efficient route toward the synthesis of a plethora of heterocyclic rings. Herein, we report an efficacious, nickel-catalyzed synthesis of two important heterocycles such as quinoline and quinoxaline. The catalyst is molecularly defined, is phosphine-free, and can operate at a mild reaction temperature of 80 °C. Both the heterocycles can be easily assembled via double dehydrogenative coupling, starting from 2-aminobenzyl alcohol/1-phenylethanol and diamine/diol, respectively, in a shorter span of reaction time. This environmentally benign synthetic protocol employing an inexpensive catalyst can rival many other transition-metal systems that have been developed for the fabrication of two putative heterocycles. Mechanistically, the dehydrogenation of secondary alcohol follows clean pseudo-first-order kinetics and exhibits a sizable kinetic isotope effect. Intriguingly, this catalyst provides an example of storing the trapped hydrogen in the ligand backbone, avoiding metal-hydride formation. Easy regeneration of the oxidized form of the catalyst under aerobic/O2 oxidation makes this protocol eco-friendly and easy to handle.

Manganese(III) Porphyrin-Catalyzed Dehydrogenation of Alcohols to form Imines, Tertiary Amines and Quinolines

Manganese(III) porphyrin chloride complexes have been developed for the first time as catalysts for the acceptorless dehydrogenative coupling of alcohols and amines. The reaction has been applied to the direct synthesis of imines, tertiary amines and quinolines where only hydrogen gas and/or water are formed as the by-product(s). The mechanism is believed to involve the formation of a manganese(III) alkoxide complex which degrades into the aldehyde and a manganese(III) hydride species. The latter reacts with the alcohol to form hydrogen gas and thereby regenerates the alkoxide complex.

Quinoline derivative synthesis method

The invention discloses a quinoline derivative synthesis method. The method comprises the steps that substitutional acetophenone, aniline and dimethyl sulfoxide perform one-pot reaction in an oxygen-containing atmosphere in the presence of a copper salt catalyst to obtain a quinoline derivative. The quinoline derivative types are enriched and more intermediates are provided for drug synthesis by adopting the method, raw materials are wide in source, the steps are simple, reaction conditions are mild, the yield is high, and the method facilitates industrial production.

Method for intermolecular cyclization synthesis of quinoline derivative

The invention discloses a method for intermolecular cyclization synthesis of a quinoline derivative. The method comprises the following step: in an atmosphere of oxygen, performing a one-pot reactionon aryl aceton, phenylamine and dimethyl sulfoxide in the presence of a ferric salt and/or ferrite catalyst, thereby obtaining the quinoline derivative. By adopting the method, the types of quinolinederivatives are enriched, a relatively large amount of intermittent are provided for medicine synthesis, and in addition, the method is wide in raw material source, simple in step, gentle in reactioncondition, high in yield and beneficial to industrial production.

Tris(pentafluorophenyl)borane-Catalyzed Acceptorless Dehydrogenation of N-Heterocycles

Catalytic acceptorless dehydrogenation is an environmentally benign way to desaturate organic compounds. This process is traditionally accomplished with transition-metal-based catalysts. Herein, a borane-catalyzed, metal-free acceptorless dehydrogenation of saturated N-heterocycles is disclosed. Tris(pentafluorophenyl)borane was identified as a versatile catalyst, which afforded several synthetically important N-heteroarenes in up to quantitative yield. Specifically, the present metal-free catalytic system exhibited a uniquely high tolerance toward sulfur functionalities, and demonstrated superior reactivity in the synthesis of benzothiazoles compared to conventional metal-catalyzed systems. This protocol can thus be regarded as the first example of metal-free acceptorless dehydrogenation in synthetic organic chemistry.

Transition-metal-free synthesis of quinolines from 2-nitrobenzyl alcohol in water

A method for the synthesis of quinolines from cheap and readily available 2-nitrobenzyl alcohol without a transition-metal catalyst in water has been developed, providing a convenient method for accessing quinolines. The reaction features an intramolecular redox process, which generates the key intermediate leading to product formation.