- Reactions of 3-arylpropenenitriles with arenes under superelectrophilic activation conditions: Hydroarylation of the carbon-carbon double bond followed by cyclization into 3-arylindanones
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Reactions of 3-arylpropenenitriles [ArCH[dbnd]CHCN] with arenes [Ar'H] under the superelectrophilic activation conditions with Br?nsted superacid TfOH (CF3SO3H) or strong Lewis acid AlBr3 result, first, in the formation of products of hydroarylation of the carbon-carbon double bond, 3,3-diarylpropanenitriles [Ar(Ar’)CHCH2CN]. Reactions may go further in TfOH leading to 3-arylindanones, as products of intramolecular aromatic acylation by the electrophilically activated nitrile group. Intermediate cationic species, derived at the protonation of the starting 3-arylpropenenitriles onto the carbon of C[dbnd]C bond and the nitrile nitrogen, have been studied by DFT calculation. A plausible reaction mechanism including the formation of highly reactive dications [(Ar)HC+–CH2C+ = NH] has been proposed. The obtained 3,3-diarylpropanenitriles have been transformed into pharmaceutically valuable 5-(2,2-diarylethyl)-1H-tetrazoles [Ar(Ar’)CHCH2Tetr] and 3-diarylpropylamines [Ar(Ar’)CH(CH2)2NH2] by the reactions with NaN3 and LiAlH4 correspondingly.
- Gorbunova, Yelizaveta,Zakusilo, Dmitriy N.,Boyarskaya, Irina A.,Vasilyev, Aleksander V.
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- Transition-metal-free Intramolecular C-H amination of sulfamate esters and: N -alkylsulfamides
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The transition-metal-free intramolecular C-H amination of sulfamate esters using iodine oxidants, tert-butyl hypoiodite (t-BuOI) and N-iodosuccinimide (NIS) is reported. A method using NIS was also successfully applied to the oxidative cyclization of N-alkylsulfamides.
- Kiyokawa, Kensuke,Nakamura, Shogo,Jou, Keisuke,Iwaida, Kohji,Minakata, Satoshi
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supporting information
p. 11782 - 11785
(2019/10/02)
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- Iron and Phenol Co-Catalysis for Rapid Synthesis of Nitriles under Mild Conditions
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A mild, scalable, high yielding, and rapid route to access diverse nitriles from aldehyde oxime esters enabled by iron(III) and phenol co-catalysis has been developed. The reaction was performed at room temperature to give nitriles in excellent yield within minutes. Mechanistic studies show that the reaction may proceed through a radical process in which benzoyl aldehyde oxime is not only a substrate, but also an ancillary ligand to support iron salt in the promotion of the transformation.
- Meng, Hong,Gao, Sen,Luo, Meiming,Zeng, Xiaoming
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p. 4617 - 4623
(2019/07/15)
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- Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides
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The sustainable introduction of nitrogen moieties in the form of nitrile or amide groups in functionalized molecules is of fundamental interest because nitrogen-containing motifs are found in a large number of life science molecules, natural products and materials. Hence, the synthesis and functionalization of nitriles and amides from easily available starting materials using cost-effective catalysts and green reagents is highly desired. In this regard, herein we report the nanoscale iron oxide-catalyzed environmentally benign synthesis of nitriles and primary amides from aldehydes and aqueous ammonia in the presence of 1 bar O2 or air. Under mild reaction conditions, this iron-catalyzed aerobic oxidation process proceeds to synthesise functionalized and structurally diverse aromatic, aliphatic and heterocyclic nitriles. Additionally, applying this iron-based protocol, primary amides have also been prepared in a water medium.
- Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Sharif, Muhammad,Kalevaru, Narayana V.,Jagadeesh, Rajenahally V.
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supporting information
p. 266 - 273
(2018/01/12)
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- Immobilized NNN Pd-complex on magnetic nanoparticles: Efficient and reusable catalyst for Heck and Sonogashira coupling reactions
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A highly efficient and easily recyclable magnetic nanoparticle supported palladium catalyst was developed and applied in the Heck and Sonogashira reactions in order to show its catalytic applicability in Pd-catalyzed C-C coupling protocols. The catalyst was prepared using a simple chemical process. First, the prepared Fe3O4@SiO2 nanoparticles were reacted with (3-chloropropyl)-trimethoxysilane (3-CPTMS) in order to synthesis chloro-functionalized magnetic nanoparticles (CPS-MNPs). The substitution reaction of synthetic NNN ligand with CPS-MNPs yields the production of CPS-MNPs-NNN ligand. Finally, immobilization of palladium species on CPS-MNPs-NNN ligand surface afforded CPS-MNPs-NNN-Pd catalyst. The structure and morphology of the prepared nanocatalyst was characterized using various methods such as SEM, TEM, XPS, EDX, CHN, ICP, XRD, FT-IR and VSM techniques. The TEM images show that the sizes of the palladium catalyst are in the range of 8-15 nm. The Heck and Sonogashira coupling reactions were performed in the presence of a catalytic amount of this catalyst system (0.5 mol%) and good yields of products were obtained. Due to the magnetic nature of the catalyst it can be separated from the reaction mixture easily by applying an external magnetic field. Heterogeneity tests affirmed that the catalytic activity stayed indefectible during multiple reaction cycles.
- Dehghani Firuzabadi, Fahimeh,Asadi, Zahra,Panahi, Farhad
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p. 101061 - 101070
(2016/11/09)
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- CONTROLLED DRUG RELEASE FROM SOLID SUPPORTS
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The invention relates to solid supports useful in medical applications that provide controlled release of drugs, such as peptides, nucleic acids and small molecules. The drugs are covalently coupled to the solid support through a linkage that releases the drug or a prodrug through controlled beta elimination.
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Page/Page column 31-32
(2011/11/30)
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- CONTROLLED RELEASE FROM MACROMOLECULAR CONJUGATES
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The invention relates to conjugates of macromolecular carriers and drugs comprising linkers that release the drug or a prodrug through rate-controlled beta-elimination, and methods of making and using the conjugates.
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Page/Page column 24-25
(2011/11/30)
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- Mizoroki-Heck type arylation of alkenes using aroyl chlorides under base-free conditions
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The Mizoroki-Heck type arylation of alkenes with aroyl chlorides accompanied by decarbonylation efficiently proceeds in the presence of a palladium catalyst system, PdCl2(PhCN)2/(PhCH 2)Bu3NCl, even without adding any base. The products can be isolated by a very simple procedure.
- Sugihara, Toru,Satoh, Tetsuya,Miura, Masahiro
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p. 8269 - 8271
(2007/10/03)
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- SELECTIVE PREPARATION OF NON-SYMMETRICALLY SUBSTITUTED DIVINYLBENZENES BY PALLADIUM-CATALYSED ARYLATIONS OF ALKENES WITH BROMOBENZOIC ACID DERIVATIVES
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Palladium-catalysed arylation of alkenes with the three bromobenzoic acids or their acyl chlorides provides an efficient and selective method for the preparation of non-symmetrically substituted divinylbenzene derivatives.In the presence of palladium acet
- Spencer, Alwyn
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p. 323 - 332
(2007/10/02)
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