- Site-Selective Pd-Catalyzed C(sp3)?H Arylation of Heteroaromatic Ketones
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A ligand-controlled site-selective C(sp3)?H arylation of heteroaromatic ketones has been developed using Pd catalysis. The reaction occurred selectively at the α- or β-position of the ketone side-chain. The switch from α- to β-arylation was realized by addition of a pyridone ligand. The α-arylation process showed broad scope and high site- and chemoselectivity, whereas the β-arylation was more limited. Mechanistic investigations suggested that α-arylation occurs through C?H activation/oxidative addition/reductive elimination whereas β-arylation involves desaturation and aryl insertion.
- Kudashev, Anton,Baudoin, Olivier
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supporting information
p. 17688 - 17694
(2021/11/16)
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- One-Pot Conversion of Allylic Alcohols to α-Methyl Ketones via Iron-Catalyzed Isomerization-Methylation
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A one-pot iron-catalyzed conversion of allylic alcohols to α-methyl ketones has been developed. This isomerization-methylation strategy utilized a (cyclopentadienone)iron(0) carbonyl complex as precatalyst and methanol as the C1 source. A diverse range of allylic alcohols undergoes isomerization-methylation to form α-methyl ketones in good isolated yields (up to 84% isolated yield).
- Latham, Daniel E.,Polidano, Kurt,Williams, Jonathan M. J.,Morrill, Louis C.
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supporting information
p. 7914 - 7918
(2019/10/16)
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- Pd-Catalyzed Alkylation of (Iso)quinolines and Arenes: 2-Acylpyridine Compounds as Alkylation Reagents
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The first Pd-catalyzed alkylation of (iso)quinolines and arenes is reported. The readily available and bench-stable 2-acylpyridine compounds were used as an alkylation reagent to form the structurally versatile alkylated (iso)quinolines and arenes. The method affords a convenient pathway for the introduction of alkyl groups into organic molecules.
- Wu, Qingsong,Han, Shuaijun,Ren, Xiaoxiao,Lu, Hongtao,Li, Jingya,Zou, Dapeng,Wu, Yangjie,Wu, Yusheng
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supporting information
p. 6345 - 6348
(2018/10/20)
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- Iron-Catalyzed Methylation Using the Borrowing Hydrogen Approach
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A general iron-catalyzed methylation has been developed using methanol as a C1 building block. This borrowing hydrogen approach employs a Kn?lker-type (cyclopentadienone)iron carbonyl complex as catalyst (2 mol %) and exhibits a broad reaction scope. A variety of ketones, indoles, oxindoles, amines, and sulfonamides undergo mono- or dimethylation in excellent isolated yields (>60 examples, 79% average yield).
- Polidano, Kurt,Allen, Benjamin D. W.,Williams, Jonathan M. J.,Morrill, Louis C.
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p. 6440 - 6445
(2018/07/25)
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- Rhodium Catalyzed Asymmetric Hydrogenation of 2-Pyridine Ketones
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Catalyzed by [Rh(COD)Binapine]BF4, the asymmetric hydrogenation of 2-pyridine ketones has been achieved with excellent enantioselectivities (enantiomeric excesses up to 99%) under mild conditions. This method is suitable for various kinds of 2-pyridine ketones and their derivatives. A number of enantiomerically pure chiral 2-pyridine-aryl/alkyl alcohols were prepared through hydrogenation, which can be used directly in organic synthesis.
- Yang, Hailong,Huo, Ningning,Yang, Ping,Pei, Hao,Lv, Hui,Zhang, Xumu
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supporting information
p. 4144 - 4147
(2015/09/15)
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- Double duty for cyanogen bromide in a cascade synthesis of cyanoepoxides
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An unprecedented reaction mode of cyanogen bromide has been discovered. Under basic conditions, cyanogen bromide acts as an equivalent of both Br + and CN- to convert enolizable ketones into the corresponding cyanoepoxides in good yields. This unique reaction mode provides new, one-pot access to densely substituted cyanoepoxides from easily available ketones (see scheme). Copyright
- Li, Zhou,Gevorgyan, Vladimir
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p. 2808 - 2810
(2011/05/05)
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- 2-Pyridyl and 3-pyridylzinc bromides: direct preparation and coupling reaction
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A facile synthetic approach to the direct preparation of 2-pyridyl and 3-pyridylzinc bromides has been demonstrated using Rieke zinc with 2-bromopyridine and 3-bromopyridine, respectively. A variety of different electrophiles have been coupled with the resulting organozinc reagents to give the corresponding cross-coupling products in moderate to good yields.
- Kim, Seung-Hoi,Rieke, Reuben D.
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supporting information; experimental part
p. 3135 - 3146
(2010/06/13)
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- A facile synthetic route for 2-pyridyl derivatives: direct preparation of a stable 2-pyridylzinc bromide and its copper-free and pd-catalyzed coupling reactions
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Direct preparation of 2-pyridylzinc bromide has been developed. Interestingly, the subsequent coupling reactions with acid chlorides have been carried out without any transition metal catalyst. 2-Pyridylaryl compounds, symmetrical and unsymmetrical 2,2′-b
- Kim, Seung-Hoi,Rieke, Reuben D.
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supporting information; experimental part
p. 5329 - 5331
(2009/12/06)
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- Synthesis, structure-activity relationships, and antitumor studies of 2-benzoxazolyl hydrazones derived from alpha-(N)-acyl heteroaromatics
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Recently we have described the antitumor activities of 2- benzoxazolylhydrazones derived from 2-formyl and 2-acetylpyridines. In search of a more efficacious analogue, compounds in which the 2-acetylpyridine moiety has been replaced by 2-acylpyridine and α-(N)-acetyldiazine/quinoline groups have been synthesized. The 2-acylpyridyl hydrazones inhibited in vitro cell proliferation in the nM range, whereas the hydrazones derived from the α-(N)-acetyldiazines/quinolines inhibited cell growth in the μM range. Compounds tested in the NCI-60 cell assay were effective inhibitors of leukemia, colon, and ovarian cancer cells. E-13k [N-benzoxazol-2-yl-N′-(1- isoquinolin-3-yl-ethylidene)-hydrazine] inhibited the proliferation of MCF-7 breast carcinoma cells more efficiently than nontransformed MCF-10A cells. It is not transported by P-glycoprotein and a weak MRP substrate. Increased concentrations of serum or α1-acid glycoprotein did not reduce the antiproliferative activity of the compound. In the in vivo hollow fiber assay, E-13k achieved a score of 24, with a net cell kill of OVCAR-3 (ovarian) and SF2-95 (CNS) tumor cells.
- Easmon, Johnny,Pürstinger, Gerhard,Thies, Katrin-Sofia,Heinisch, Gottfried,Hofmann, Johann
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p. 6343 - 6350
(2007/10/03)
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- A new and highly efficient water-soluble copper complex for the oxidation of secondary 1-heteroaryl alcohols by tert-butyl hydroperoxide
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The water-soluble copper complex generated in situ from CuCl2 and 2,2′-biquinoline-4,4′-dicarboxylic acid dipotassium salt (BQC), has been revealed as a highly efficient and selective catalyst for the oxidation of secondary 1-heteroaryl alcohols to the corresponding heteroaromatic ketones with aqueous tert-butyl hydroperoxide, under mild conditions. The catalytic system is compatible with different heterocycles such as pyridines, pyrroles, indoles, thiophens, furans, thiazoles, and imidazoles.
- Boudreau, Josée,Doucette, Mike,Ajjou, Abdelaziz Nait
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p. 1695 - 1698
(2007/10/03)
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- Synthesis and properties of N-hydroxylamine and heterocyclic derivatives based on it
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N-hydroxylamine, a new representative of the series of α-hydroxylamino oximes, was synthesized.Based on this compound, 3-imidazoline 3-oxide and 2-imidazoline 3-oxide derivatives were obtained, and some of their chemical properties were investigated. - Keywords: α-hydroxylamino oximes, N-hydroxylamine; 3-imidazoline 3-oxides; methylene nitrone, nitrones, nitroxyl radicals; pyridine.
- Voinov, M. A.,Volodarsky, L. B.
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p. 126 - 132
(2007/10/03)
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- SYNTHESIS OF ISOPROPYL AND TERT-BUTYL PYRIDYL KETONES BY ALKYLATION OF ACETYLPYRIDINES WITH METHYL IODIDE USING PHASE TRANSFER CATALYSIS
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Isomeric acetylpyridines undergo regiospecific alkylation with methyl iodide under solid/liquid phase transfer conditions (aromatic solvent/KOH/18-crown-6) to give the corresponding isopropyl and/or tert-butyl pyridyl ketones, depending on reaction conditions.
- Rubina, K.,Goldberg, Yu.,Shymanska, M.
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p. 2489 - 2500
(2007/10/02)
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- A New Synthesis of Aryl Hetaryl Ketones via SRN1 Reaction of Halogenated Heterocycles withPotassiophenylacetonitrile Followed by Phase-Transfer Catalyzed Decyanation
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Reaction of halogenated pyridines, quinolines, pyrimidines, and pyrazines with potassiophenylacetonitrile (5) in liquid ammonia under near-uv irradiation affords secondary nitriles, which then undergo oxidative decyanation under phase-transfer catalytic conditions to afford aryl hetaryl ketones in excellent yields.
- Hermann, Christine K. F.,Sachdeva, Yesh P.,Wolfe, James F.
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p. 1061 - 1065
(2007/10/02)
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