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Catalytic 1,4-selective hydrosilylation of pyridines and benzannulated congeners

Radically different! The hydrosilylation of pyridines and quinolines is strictly 1,4-selective and likely involves an ionic one-step rather than the established radical two-step hydride transfer from a ruthenium(II) hydride complex onto the respective pyridinium and quinolinium ion intermediates (see scheme; ArF=3,5-(CF3)2C6H 3). Even 4-substituted substrates react highly regioselectively. Isoquinolines yield the 1,2-reduced heterocycles.

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Reference£º
Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem

 

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Enantioselective thiourea-catalyzed acyl-Mannich reactions of isoquinolines

(Chemical Equation Presented) Inexpensive aromatic feedstocks are substrates for highly enantioselective acylative Mannich reactions catalyzed by a thiourea chiral hydrogen-bond donor 1. This methodology provides access to useful 1-substituted dihydroisoquinolines (see scheme; TrocCl = 2,2,2-trichloroethyl chloroformate, TBS = tert-butyldimethylsilyl), which serve as precursors to enantioenriched 1-substituted tetrahydroisoquinolines.

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Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem

 

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Deaminative Strategy for the Visible-Light-Mediated Generation of Alkyl Radicals

A deaminative strategy for the visible-light-mediated generation of alkyl radicals from redox-activated primary amine precursors is described. Abundant and inexpensive primary amine feedstocks, including amino acids, were converted in a single step into redox-active pyridinium salts and subsequently into alkyl radicals by reaction with an excited-state photocatalyst. The broad synthetic potential of this protocol was demonstrated by the alkylation of a number of heteroarenes under mild conditions.

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Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem

 

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Imidazole and imidazoline derivatives and uses thereof

This invention is directed to novel imidazole and imidazoline derivatives which are selective agonists for cloned human alpha2 adrenergic receptors. This invention is also related to the use of these compounds for the treatment of any disease where modulation of the alpha2 receptors may be useful. The invention further provides for a pharmaceutical composition comprising a therapeutically effective amount of the above-defined compounds and a pharmaceutically acceptable carrier.

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Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem

 

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In vitro structure-activity relationship and in vivo characterization of 1-(aryl)-3-(4-(amino)benzyl)urea transient receptor potential vanilloid 1 antagonists

The synthesis and structure-activity relationship of 1-(aryl)-3-(4-(amino) benzyl)urea transient receptor potential vanilloid 1 (TRPV1) antagonists are described. A variety of cyclic amine substituents are well tolerated at the 4-position of the benzyl group on compounds containing either an isoquinoline or indazole heterocyclic core. These compounds are potent antagonists of capsaicin activation of the TRPV1 receptor in vitro. Analogues, such as compound 45, have been identified that have good in vivo activity in animal models of pain. Further optimization of 45 resulted in compound 58 with substantially improved microsome stability and oral bioavailability, as well as in vivo activity.

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Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem

 

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N-Methylquinolinium derivatives for photonic applications: Enhancement of electron-withdrawing character beyond that of the widely-used N-methylpyridinium

A series of pi-conjugated styryl quinolinium push-pull chromophores have been designed and synthesized in order to examine the electron-withdrawing strength of various quinolinium electron acceptor groups, and their influence on the photophysical properties and in particular on the second-order nonlinear optical response. The static molecular first hyperpolarizabilities measured by long-wavelength hyper-Rayleigh scattering are found to follow the order of the electron withdrawing strength of their acceptor groups as determined by NMR analysis. The quinolinium chromophores based on the strongest electron acceptor groups (1,2- and 1,4-dimethylquinolinium) exhibit remarkably large first hyperpolarizability values of 233 and 256 ¡Á 10-30esu respectively, which is higher than that of the well-known and widely-used pyridinium analogue 4-(4-(dimethylamino)styryl)-1-methylpyridinium 4-methylbenzenesulfonate with first hyperpolarizability = 183 ¡Á 10-30esu. The dimethylquinolinium electron acceptor groups exhibit increased electron-withdrawing strength compared to the dimethylpyridinium group used in 4-(4-(dimethylamino)styryl)-1-methylpyridinium 4-methylbenzenesulfonate, and therefore have a high potential for photonic applications.

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Reference£º
Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem

 

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REACTION OF BENZYL KETONES WITH NITRILES IN PRESENCE OF POCl3

The reaction of benzyl ketones with nitriles in presence of POCl3 has been examined.It has been found that intermediate N-styrylimidoyl dichlorophosphates formed under reaction conditions undergo further reactions to isoquinoline and pyrimidine derivatives and form the products of fragmentation and condensation.The effect of structure of the substrates on the relative ratios of the products formed has been discussed.

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Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem

 

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Minisci-Type C?H Cyanoalkylation of Heteroarenes Through N?O/C?C Bonds Cleavage

A visible-light-induced C?H cyanoalkylation of heteroarenes was described, in which cycloketone oximes were readily transformed into carbon-centered radicals with a terminal cyano-group via N?O/C?C bonds cleavage in one phtochemical step. This reaction protocol displayed a broad substrate scope of heterocycle compounds, and it provided a promising strategy for the installation of cyanoalkyl groups onto heteroarenes.

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Reference£º
Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem

 

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Asymmetric synthesis of isoquinoline derivatives from amino acids

Reaction of isoquinolines 1 with N-arylsulfonylamino acid fluorides 2 provides a highly stereoselective access to new dihydroimidazo[2,1-a] isoquinolin-3-ones 5 via intermediate N-acylisoquinolinium salts 3. Addition reactions to the enamine double bond, such as hydrogenation or epoxidation with dimethyldioxirane, leads to tetrahydroimidazo[2,1-a]isoquinoline-3-ones 6, 7 and oxiranes 8, respectively. Opening of the oxirane ring of the 8 with nucleophiles allows the synthesis of hydroxytetrahydroimidazo[2,1-a]isoquinolin- 3-ones 10 or 12 or of the polycyclic 1,4-dioxane 13 in high stereoselectivity. The regioselectivity of the oxiran ring opening depends on the kind of nucleophile and the conditions. Reaction of dihydroisoquinoline with O-TBDMS-mandelic acid chloride 15 leads to a tetrahydrooxazolo[2,3-a] isoquinoline 17 with opposite facial selectivity as compared with dihydroimidazo[2,1-a]isoquinolin-3-ones 5. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.

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Reference£º
Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem

 

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Photocatalytic C-H silylation of heteroarenes by using trialkylhydrosilanes

The efficient and selective C-H silylation of heteroarenes, especially the pharmaceutically relevant electron-deficient heteroarenes, represents a great challenge in organic synthesis. Herein we wish to report a distinctive visible light-promoted photocatalytic C-H silylation approach that enables the direct coupling of trialkylhydrosilanes with both electron-deficient and -rich heteroarenes as well as with cyano-substituted arenes in moderate to high yields and with good regioselectivity. The protocol features operational simplicity, mild reaction conditions, and the use of safe and readily available Na2S2O8, bis(trimethylsilyl) peroxide (BTMSPO) or iPr3SiSH as the radical initiators. Notably, the challenging bulky and inert trialkylhydrosilanes, such as (t-butyldimethyl)silane (tBuMe2SiH) and (triisopropyl)silane (iPr3SiH), work smoothly with the protocol. Moreover, despite the higher stability of tBuMe2Si silylation products, our studies revealed their great reactivity and versatility in diverse C-Si-based chemical transformations, providing an operationally simple, low-cost, and environmentally benign synthetic technology for molecule construction and elaboration.

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Reference£º
Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem