- Catalytic Asymmetric Addition of Diorganozinc Reagents to Pyrazole-4,5-Diones and Indoline-2,3-Diones
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The catalytic enantioselective diorganozinc additions to cyclic diketones including pyrazolin-4,5-diones and isatins have been developed. In the presence of morpholine-containing chiral amino alcohol ligand, the corresponding chiral cyclic tertiary alcohols were produced in good to excellent yields (up to 97 %) and enantioselectivities (up to 95 % ee). The notable feature of this protocol includes its mild reaction conditions, Lewis acid additives free and broad functional group tolerance.
- Wang, Rong-Hui,Li, Ya-Ling,He, Hong-Jiao,Xiao, You-Cai,Chen, Fen-Er
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supporting information
p. 4302 - 4306
(2021/02/16)
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- Experimental and Computational Studies on Cp*CyRh(III)/KOPiv-Catalyzed Intramolecular Dehydrogenative Cross-Couplings for Building Eight-Membered Sultam/Lactam Frameworks
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Described herein is an unusual Cp*CyRh(III)-catalyzed intramolecular site-specific aryl C-H annulation, a highly chemoselective protocol providing direct access to eight-membered sultams/lactams with broad substrate/functional group tolerance. Experimental and computational studies reveal that such a transformation involves a unique PivOH-assisted aryl C-H activation/alkene insertion/β-H elimination/hydrogen-transfer process involving the Rh(III)-hydride species as the active intermediate with the concomitant release of H2 as the major byproduct, thus enabling the developed Cp*CyRh(III) catalysis with redox-neutral and highly atom-economical features.
- Li, Liping,Gao, Hui,Sun, Ming,Zhou, Zhi,Yi, Wei
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supporting information
p. 5473 - 5478
(2020/07/14)
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- One-Pot Synthesis of Spirocyclopenta[ a]indene Derivatives via a Cascade Ring Expansion and Intramolecular Friedel-Crafts-Type Cyclization
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A one-pot efficient synthetic approach for the rapid construction of spirocyclopenta[a]indene derivatives has been developed via an iodine-initiated cascade ring expansion and intramolecular Friedel-Crafts-type cyclization from propargyl alcohol-tethered alkylidenecyclobutanes under mild conditions with broad substrate scope. This cascade process can be elegantly conducted on a gram scale. A plausible reaction mechanism has been proposed on the basis of a series of deuterium labeling and control experiments.
- Li, Quanzhe,Liu, Jiaxin,Wei, Yin,Shi, Min
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supporting information
p. 2438 - 2455
(2020/01/31)
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- Pd-catalyzed regiodivergent synthesis of diverse oxindoles enabled by the versatile heck reaction of carbamoyl chlorides
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We report herein a miscellaneous oxindole synthesis bearing an all-carbon quaternary center, enabled by Pd-catalyzed intramolecular cyclization followed by multiple intermolecular Heck reactions of both easily accessible alkene-tethered carbamoyl chlorides and olefins. This protocol obviates the use of prefunctionalized olefinic reagents, exhibits excellent functional group tolerance, and features fascinating reactive versatility.
- Wu, Xianqing,Tang, Zaiquan,Zhang, Chengxi,Wang, Chenchen,Wu, Licheng,Qu, Jingping,Chen, Yifeng
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supporting information
p. 3915 - 3921
(2020/06/08)
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- Copper-catalyzed tandem annulation/enol nucleophilic addition to access multisubstituted indoles
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A method to access various multisubstituted indoles from propargylic alcohols and readily available enol nucleophiles by copper-catalyzed tandem annulation/enol nucleophilic addition has been developed. Compared to the expensive metal catalysts such as platinum, gold, silver, and palladium used previously, the most economical copper(i) catalyst could achieve this reaction efficiently. The fused heterocyclic compounds, pyrrolo[1,2-a] indoles, could be afforded by further transformation of the products. The allyl cation intermediate may be involved in the mechanism.
- Song, Wangze,Li, Ming,He, Junnan,Li, Junhao,Dong, Kun,Zheng, Yubin
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supporting information
p. 2663 - 2669
(2019/03/13)
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- Catalyst-free geminal aminofluorination of ortho-sulfonamide-tethered alkylidenecyclopropanes via a Wagner-Meerwein rearrangement
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A catalyst-free intramolecular geminal aminofluorination of ortho-sulfonamide-tethered alkylidenecyclopropanes has been developed. The reaction proceeded through two SET processes with Selectfluor to give a fluorinated cyclopropylcarbinyl cation and a further Wagner-Meerwein rearrangement to generate a cyclobutyl carbocation, which undergoes intramolecular nucleophilic capture by amide to forge fluorinated cyclobuta[b]indoline derivatives. A polycyclic multi-fluorinated byproduct was also formed through a Ritter-type reaction in some cases.
- Fan, Xing,Wang, Qiang,Wei, Yin,Shi, Min
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supporting information
p. 10503 - 10506
(2018/09/21)
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- Direct Electrophilic C?H Alkynylation of Unprotected 2-Vinylanilines
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Unprotected aromatic amines can be used as directing groups in metal-catalyzed C?H alkynylations of alkenes. By using low amounts of an IrIIIcatalyst in combination with alkynylbenziodoxolones as electrophilic alkyne-transfer reagents, highly desirable 1,3-enynes were isolated in excellent yields of up to 98 % with Z stereoselectivity. A broad substrate scope as well as the high synthetic utility of the 1,3-enynes render this new method an efficient approach for the synthesis of five- and six-membered heterocycles. Further derivatizations of the 1,3-enynes to highly substituted quinolines through AuI- and N-bromosuccinimide-mediated exo-dig cyclizations were demonstrated.
- Caspers, Lucien D.,Finkbeiner, Peter,Nachtsheim, Boris J.
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supporting information
p. 2748 - 2752
(2017/03/08)
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- NH2-directed C-H alkenylation of 2-vinylanilines with vinylbenziodoxolones
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The first directing-group-mediated C-H alkenylation with alkenyl-λ3-iodanes as electrophilic alkene-transfer reagents has been developed. The application of free aromatic amines as challenging but synthetically valuable directing groups in combination with an IrIII catalyst enabled the synthesis of highly desirable 1, 3- dienes in excellent yields of up to 98% with high to perfect (Z, E) stereoselectivity. A broad substrate scope and further synthetic modifications are demonstrated.
- Boelke, Andreas,Caspers, Lucien D.,Nachtsheim, Boris J.
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supporting information
p. 5344 - 5347
(2017/11/07)
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- A 1H-indazole derivatives preparation method
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The invention provides a method for preparing 3-methyl-5-R-1H-indazole easily, safely and efficiently without performing any hydrazine hydrate reflux heating reaction or purifying a product and making the product pass through a column. The method at least comprises the following steps of: a, performing a diazo-reaction on 2-amino-5-R-hypnone serving as a raw material or an intermediate under the condition of an acid solution to generate a diazo salt; b, slowly adding a stannous chloride-hydrate hydrochloric acid solution into the diazo salt obtained in the step a for reacting to generate a 3-methyl-5-R-1H-indazole solution; and c, cooling the solution obtained in the step b under the condition that the pH value is 8-9, and precipitating a product out, wherein R in the steps above represents H or a halogen element.
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Paragraph 0039; 0040
(2017/02/24)
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- Photo-Fries rearrangement of aryl acetamides: Regioselectivity induced by the aqueous micellar green environment
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Photochemical reactions tend to give more than one photoproduct. However, such a reaction can be a powerful synthetic tool when it is possible to conduct it in regioselective conditions yielding a single photoproduct. Water-surfactant solutions as reaction media can be considered as an approach in this context because they show products with different features than those from isotropic solutions. Here we describe results obtained from studying the effect on the prototypical photoreaction, known as the photo-Fries reaction of several substituted acetanilides and α-naphthyl acetamide within surfactant micelles (ionic and non-ionic micelles). This reaction involves homolytic cleavage of a C-N bond to yield a singlet radical pair. The surfactant micelles control the rotational and translational mobility of the radical pair, resulting in noticeable photoproduct selectivity.
- Iguchi, Daniela,Erra-Balsells, Rosa,Bonesi, Sergio M.
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p. 105 - 116
(2016/01/20)
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- Primary amino acid catalyzed asymmetric intramolecular Mannich reaction for the synthesis of 2-aryl-2,3-dihydro-4-quinolones
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Primary amino acids are found to be good enantioselective catalysts for the direct asymmetric Mannich reaction between 2-amino acetophenone and aldehydes. The 2-aryl-2,3-dihydro-4-quinoline products are obtained in moderate to good yields and good to high enantioselectivities with 10 mol% of the primary amino acid catalyst under mild reaction conditions.
- Mondal, Buddhadeb,Pan, Subhas Chandra
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supporting information
p. 9789 - 9792
(2015/01/09)
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- Br?nsted acid/rhodium(II) cooperative catalytic asymmetric three-component aldol-type reaction for the synthesis of 3-amino oxindoles
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Cooperation is key! Chiral Br?nsted acid/rhodium(II) cooperative catalysis enabled an enantioselective three-component aldol-type reaction of 3-diazo oxindoles and anilines with glyoxylates to give highly functionalized and structurally diverse 3-amino oxindoles in high stereoselectivity (>20:1 d.r., 99 % ee; see scheme). Copyright
- Ren, Lei,Lian, Xiao-Lei,Gong, Liu-Zhu
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supporting information
p. 3315 - 3318
(2013/07/11)
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- Ru(ii)-catalyzed intermolecular ortho-C-H amidation of aromatic ketones with sulfonyl azides
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Ru(ii)-catalyzed intermolecular ortho-C-H amidation of weakly coordinating aromatic ketones with sulfonyl azides is reported. The developed reaction protocol can be extended to various substituted aromatic ketones to afford a wide range of desired C-N bond formation products in good yields.
- Bhanuchandra,Ramu Yadav,Rit, Raja K.,Rao Kuram, Malleswara,Sahoo, Akhila K.
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supporting information
p. 5225 - 5227
(2013/06/27)
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- Selenium-promoted intramolecular oxidative amidation of 2-(arylamino)acetophenones for the synthesis of N-arylisatins
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A convenient method for the synthesis of N-arylisatins from 2-(arylamino)acetophenones by using SeO2 as an oxidant is described. Various substituted N-arylisatins were selectively obtained in good to excellent yields. The reaction tolerates a wide range of functionalities. Copyright
- Liu, Yong,Chen, Hui,Hu, Xiong,Zhou, Wang,Deng, Guo-Jun
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supporting information
p. 4229 - 4232
(2013/07/26)
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- Synthesis of functionalized quinolines and benzo[c][2,7]naphthyridines based on a photo-fries rearrangement
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An efficient one-pot method for the synthesis of functionalized quinolines and tetrahydronaphthyridines has been developed. The photo-Fries rearrangement of p-substituted anilides afforded differently substituted o-amino ketones that reacted in situ with acetylenic Michael acceptors such as dimethyl acetylenedicarboxylate (DMAD) to give 6,4-disubstituted quinoline 2,3-dicarboxylates. Starting from anilides derived from β-alanine, a naphthyridine nucleus can also be assembled.
- Guerrini, Giacomo,Taddei, Maurizio,Ponticelli, Fabio
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experimental part
p. 7597 - 7601
(2011/11/12)
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- A new general approach to 4-substituted-3-halo-2-quinolones
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A general procedure for the preparation of 4-substituted-3-halo-2-quinolones (halo = F, Cl, Br) utilizing 2-halo diethylphosphonoacetic acids (halo = F, Cl, Br) and o-aminophenylketones as the starting materials is described. The title compounds are obtained by an intramolecular Horner-Wadsworth-Emmons olefination of halogen-containing N-acyl-o-aminophenylketones. The transformation process is generally applicable under mild conditions.
- Zhao, Shuai,He, Yan-hong,Wu, Di,Guan, Zhi
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experimental part
p. 597 - 605
(2010/06/21)
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- Synthesis of 4-alkylidene-4H-3,1-benzoxazine derivatives by acid-catalyzed cyclization of 2-isocyanophenyl ketones in the presence of a vinyl ether
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2-(1-Alkoxyalkyl)-4-alkylidene-4H-3,1-benzoxazines are conveniently prepared by the reaction of 1-(2-isocyanophenyl) ethanones or 1-(2-isocyanophenyl)propan-1-ones with a vinyl ether, such as 2-methoxypropene or ethyl vinyl ether, in the presence of a catalytic amount of (±)-camphor-10-sulfonic acid. Georg Thieme Verlag Stuttgart.
- Kobayashi, Kazuhiro,Okamura, Yuta,Konishi, Hisatoshi
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experimental part
p. 1494 - 1498
(2009/12/06)
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- Discovery of novel benzoxazinones as potent and orally active long chain fatty acid elongase 6 inhibitors
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A series of benzoxazinones was synthesized and evaluated as novel long chain fatty acid elongase 6 (ELOVL6) inhibitors. Exploration of the SAR of the UHTS lead 1a led to the identification of (S)-1y that possesses a unique chiral quarternary center and a
- Mizutani, Takashi,Ishikawa, Shiho,Nagase, Tsuyoshi,Takahashi, Hidekazu,Fujimura, Takashi,Sasaki, Takahide,Nagumo, Akira,Shimamura, Ken,Miyamoto, Yasuhisa,Kitazawa, Hidefumi,Kanesaka, Maki,Yoshimoto, Ryo,Aragane, Katsumi,Tokita, Shigeru,Sato, Nagaaki
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supporting information; experimental part
p. 7289 - 7300
(2010/06/16)
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- N-PHENYL-1,1,1-TRIFLUOROMETHANESULFONAMIDE HYDRAZONE DERIVATIVE COMPOUNDS AND THEIR USAGE IN CONTROLLING PARASITES
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Novel N-phenyl-1,1,1-trifluoromethanesulfonamide compounds useful for controlling endo and/or ectoparasites in the environment are provided, together with methods of making the same, and methods of using the inventive compounds to treat parasite infestations in vivo and ex vivo.
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Page/Page column 26
(2008/06/13)
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- Novel and convenient synthesis of substituted quinolines by copper- or palladium-catalyzed cyclodehydration of 1-(2-aminoaryl)-2-yn-1-ols
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(Chemical Equation Presented) A general and convenient synthesis of substituted quinolines by regioselective copper- or palladium-catalyzed 6-endo-dig cyclization-dehydration of 1-(2-aminoaryl)-2-yn-1-ols is reported. The crude substrates were easily obtained by the Grignard reaction between the appropriate alkynylmagnesium bromide and 2-aminoaryl ketones and could be used without further purification for the subsequent cyclization step. Heteroannulation reactions were carried out in MeOH or DME as the solvent at 60 or 100°C in the presence of CuCl2 or PdX2 (in conjunction with 10 equiv of KX, X = Cl, I) as the catalyst to afford the quinoline derivatives in good to excellent isolated yields based on starting 1-(2-aminoaryl)-2-yn-1-ols (66-90%).
- Gabriele, Bartolo,Mancuso, Raffaella,Salerno, Giuseppe,Ruffolo, Giuseppe,Plastina, Pierluigi
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p. 6873 - 6877
(2008/02/10)
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- Acyl indoles, compositions containing such compounds and methods of use
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The present invention relates to substituted indoles, compositions containing such compounds and methods of treatment The compounds are glucagon receptor antagonists and thus are useful for treating, preventing or delaying the onset of type 2 diabetes mellitus and related conditions.
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Page/Page column 33
(2008/06/13)
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- Identification of anthranilic acid derivatives as a novel class of allosteric inhibitors of hepatitis C NS5B polymerase
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A series of potent anthranilic acid-based inhibitors of the hepatitis C NS5B polymerase has been identified. The inhibitors bind to a site on NS5B between the thumb and palm regions adjacent to the active site as determined by X-ray crystallography of the enzyme-inhibitor complex. Guided by both molecular modeling and traditional SAR, the enzyme activity of the initial hit was improved by approximately 100-fold, yielding a series of potent and selective NS5B inhibitors with IC50 values as low as 10 nM. These compounds were also inhibitors of the HCV replicon in cultured HUH7 cells.
- Nittoli, Thomas,Curran, Kevin,Insaf, Shabana,DiGrandi, Martin,Orlowski, Mark,Chopra, Rajiv,Agarwal, Atul,Howe, Anita Y. M.,Prashad, Amar,Floyd, M. Brawner,Johnson, Bernard,Sutherland, Alan,Wheless, Karen,Feld, Boris,O'Connell, John,Mansour, Tarek S.,Bloom, Jonathan
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p. 2108 - 2116
(2008/02/06)
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- Control of parasites in animals by the use of novel trifluoromethanesulfonanilide oxime ether derivatives
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Novel trifluoromethanesulfonanilide oxime ether compounds useful for controlling endo and/or ectoparasites in the environment are provided, together with methods of making the same, and methods of using the inventive compounds to treat parasite infestations in vivo or ex vivo.
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Page/Page column 24; 4/12
(2010/10/20)
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- Fries-type rearrangement of acylanilides in the presence of ytterbium triflate
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Ytterbium triflate has been used to catalyse the Fries-type rearrangement of various acylanilides with moderate yields when lithium perchlorate was used as co-catalyst.
- Su, Weike,Jin, Can
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p. 611 - 613
(2007/10/03)
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- Antitumor Agents. 155. Synthesis and Biological Evaluation of 3',6,7-Substituted 2-Phenyl-4-quinolones as Antimicrotubule Agents
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A series of 3',6,7-substituted 2-phenyl-4-quinolones were designed and synthesized as antimitotic antitumor agents. All compounds showed cytotoxic effects (log GI50/=-4.0; log drug molar concentration required to cause 50percent inhibition) against the growth of a variety of human tumor cell lines, including those derived from solid tumors such as non-small cell lung, colon, central nervous system, ovary, prostate, and breast cancers, when evaluated in the National Cancer Institute's 60 human tumor cell line in vitro screen. The most potent compound (26) demonstrated strong cytotoxic effects with GI50 values in the nanomolar or subnanomolar range in almost all the tumor cell lines. Compound 26 was also a potent inhibitor of tubulin polymerization and radiolabeled colchicine binding to tubulin, with activity comparable to those of the potent antimitotic natural products colchicine, podophyllotoxin, and combretastatin A-4.
- Li, Leping,Wang, Hui-Kang,Kuo, Sheng-Chu,Wu, Tian-Shung,Mauger, Anthony,et al.
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p. 3400 - 3407
(2007/10/02)
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- Thermal Fries rearrangement of anilides
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Anilides undergo thermal Fries rearrangement in the presence of TiCl4, ThCl4 and ZrOCl2 to afford either para-aminoaryl ketones exclusively or ortho- and para-aminoaryl ketones in which the para-product predominates.
- Ravi, Subban,Saravanan, Nagusamy,Shanthi, Andy,Dharmaraj, Nallusamy,Lakshmanan, Akoni J
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p. 443 - 445
(2007/10/02)
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