- Copper-catalyzed tri- or tetrafunctionalization of alkenylboronic acids to prepare tetrahydrocarbazol-1-ones and indolo[2,3-a]carbazoles
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We describe a cascade strategy for tri- or tetrafunctionalization of alkenylboronic acids to prepare diverse tetrahydrocarbazol-1-ones and indolo[2,3-a]carbazoles in good yields withN-hydroxybenzotriazin-4-one (HOOBT) and arylhydrazines as oxygen and nitrogen sources, respectively. Mechanistic studies reveal that the domino reaction undergoes the copper-catalyzed Chan-Lam reaction, [2,3]-rearrangement, nucleophilic substitution, oxidation and sequential [3,3]-rearrangement over five steps in a one-pot reaction. The reaction shows a broad substrate scope and tolerates a wide range of functional groups. More importantly, the reaction is easily performed at gram scales and the product is purified by simple extraction, washing, and recrystallization without flash column chromatography. The present protocol features easily available starting materials, high site-marked functionalization, five-step cascade in one pot, multiple C-C/C-O/C-N bond formation, and diversity of indole motifs.
- Bi, Hong-Yan,Li, Cheng-Jing,Liang, Cui,Mo, Dong-Liang,Wei, Cui
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supporting information
p. 5815 - 5821
(2020/09/21)
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- Preparation method of allylboronic acid pinacol ester
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The invention provides a common preparation method of allylboronic acid pinacol ester. The common preparation method takes aliphatic ketone as a raw material and comprises the following steps: takingaliphatic ketone and p-toluenesulfonohydrazide as raw ma
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Paragraph 0006
(2019/04/06)
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- Pd-Catalyzed Heck-Type Reaction: Synthesizing Highly Diastereoselective and Multiple Aryl-Substituted P-Ligands
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In this work, an efficient palladium-catalyzed Heck-type reaction was successfully used to synthesize a wide range of monoaryl-or diaryl-substituted P-ligands with excellent yields and diastereoselectivity (up to 98% yield, dr >20:1). The preliminary mechanistic studies demonstrated that it possibly underwent a cationic Heck reaction that was assisted by silver salt, and it revealed the significant role of P(O)Ar2 for excellent yields and diastereoselectivity.
- Li, Chong,Qiang, Xiao-Yue,Qi, Zhi-Chao,Cao, Bin,Li, Jing-Yu,Yang, Shang-Dong
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supporting information
p. 7138 - 7142
(2019/09/30)
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- Palladium-Catalyzed Cross-Coupling of gem-Bis(boronates) with Aryl Halides: An Alternative to Access Quaternary α-Aryl Aldehydes
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The compounds with a quaternary α-aryl aldehyde skeleton are important units in organic chemistry. Previously, the aryl group and carbonyl group are introduced in a stepwise manner. Herein, a novel route is developed to construct the quaternary α-aryl aldehydes with gem-bis(boronates) as precursors, in which the two groups are installed simultaneously. The gem-bis(boronates) are readily available from ketones; as a result, this methodology provides a more general strategy to produce the quaternary α-aryl aldehydes with broad scopes and synthetic convenience.
- Zheng, Purui,Zhai, Yujie,Zhao, Xiaoming,Xu, Tao
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supporting information
p. 393 - 396
(2019/01/23)
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- Copper-catalyzed one-pot coupling reactions of aldehydes (ketones), tosylhydrazide and 2-amino(benzo)thiazoles: An efficient strategy for the synthesis of N-alkylated (benzo)thiazoles
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An efficient and practical C–N bond formation methodology for the synthesis of N-alkylated (benzo)thiazoles was developed, via the copper-catalyzed one-pot two-step reactions of 2-amino(benzo)thiazoles and aldehydes (ketones) with tosylhydrazide. This cross-coupling reaction proceeded smoothly and tolerated a broad range of functional groups (46 examples). A variety of functionalized N-alkylated (benzo)thiazoles were obtained in moderate to high yields. Notably, gram-scale synthesis of fanetizole (anti-inflammatory drug) was also realized through this protocol.
- Xie, Zengyang,Chen, Ruijiao,Ma, Mingfang,Kong, Lingdong,Liu, Jun,Wang, Cunde
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- Development of pyrazole and spiropyrazoline analogs as multifunctional agents for treatment of Alzheimer's disease
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Cholinergic hypothesis of Alzheimer's disease has been advocated as an essential tool in the last couple of decades for the drug development. Here in, we report de novo fragment growing strategy for the design of novel 3,5-diarylpyrazoles and hit optimization of spiropyrazoline derivatives as acetyl cholinesterase inhibitors. Both type of scaffolds numbering forty compounds were synthesized and evaluated for their potencies against AChE, BuChE and PAMPA. Introduction of lipophilic cyclohexane ring in 3,5-diarylpyrazole analogs led to spiropyrazoline derivatives, which facilitated and improved the potencies. Compound 44 (AChE = 1.937 ± 0.066 μM; BuChE = 1.166 ± 0.088 μM; hAChE = 1.758 ± 0.095 μM; Pe = 9.491 ± 0.34 × 10?6 cm s1) showed positive results, which on further optimization led to the development of compound 67 (AChE = 0.464 ± 0.166 μM; BuChE = 0.754 ± 0.121 μM; hAChE = 0.472 ± 0.042 μM; Pe = 13.92 ± 0.022 × 10?6 cm s1). Compounds 44 and 67 produced significant displacement of propidium iodide from the peripheral anionic site (PAS) of AChE. They were found to be safer to MC65 cells and decreased metal induced Aβ1-42 aggregation. Further, in-vivo behavioral studies, on scopolamine induced amnesia model, the compounds resulted in better percentage spontaneous alternation scores and were safe, had no influence on locomotion in tested animal groups at dose of 3 mg/kg. Early pharmacokinetic assessment of optimized hit molecules was supportive for further drug development.
- Gutti, Gopichand,Kumar, Devendra,Paliwal, Pankaj,Ganeshpurkar, Ankit,Lahre, Khemraj,Kumar, Ashok,Krishnamurthy, Sairam,Singh, Sushil Kumar
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- Lewis Acid Catalyzed [4 + 2] Cycloaddition of N-Tosylhydrazones with ortho-Quinone Methides
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A formal [4 + 2] cycloaddition of N-tosylhydrazones with ortho-quinone methides was developed, affording the facile synthesis of diverse 1,3-oxazine derivatives under mild conditions. In this transformation, N-tosylhydrazones are used as a 1,2-dipole synt
- Wang, Chun-Ying,Han, Jia-Bin,Wang, Long,Tang, Xiang-Ying
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p. 14258 - 14269
(2019/11/11)
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- Rapid Synthesis of N-Tosylhydrazones under Solvent-Free Conditions and Their Potential Application Against Human Triple-Negative Breast Cancer
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Some N-tosylhydrazone derivatives were effectively synthesized under solvent-free conditions by using a grinding method at room temperature. The short reaction time, clean and mild process with simple workup and easy purification of the target compounds w
- Xie, Zengyang,Song, Yuying,Xu, Lujia,Guo, Yukun,Zhang, Min,Li, Limei,Chen, Kai,Liu, Xue
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p. 977 - 983
(2018/11/27)
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- A cascade Claisen rearrangement/o-quinone methide formation/electrocyclization approach to 2H-chromenes
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A new approach has been developed for the synthesis of 8-substituted 2H-chromenes, featuring a novel cascade aromatic Claisen rearrangement/o-quinone methide formation/6π-electrocyclization. This new method was demonstrated with 28 examples tolerating different substitutions at alkenes, allylic and aromatic ring and with total syntheses of three 2H-chromene natural products.
- Song, Liyan,Huang, Fang,Guo, Liwen,Ouyang, Ming-An,Tong, Rongbiao
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supporting information
p. 6021 - 6024
(2017/07/10)
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- Zinc-promoted cyclization of tosylhydrazones and 2-(dimethylamino)malononitrile: An efficient strategy for the synthesis of substituted 1-tosyl-1: H -pyrazoles
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A Zn(OTf)2-promoted cyclization reaction of tosylhydrazones with 2-(dimethylamino)malononitrile has been successfully developed providing an efficient strategy for the synthesis of substituted 1-tosyl-1H-pyrazoles.
- Zhang, Bang-Hong,Lei, Lin-Sheng,Liu, Si-Zhan,Mou, Xue-Qing,Liu, Wei-Ting,Wang, Shao-Hua,Wang, Jie,Bao, Wen,Zhang, Kun
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supporting information
p. 8545 - 8548
(2017/08/04)
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- One-Pot Synthesis of Spirocyclic or Fused Pyrazoles from Cyclic Ketones: Calcium Carbide as the Carbon Source in Ring Expansion
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N-Tosylhydrazones generated in situ from cyclic ketones smoothly underwent a [3 + 2] cycloaddition to afford saturated spirocyclic pyrazoles and further transformed to the fused analogues via a ring expansion in certain cases. An inexpensive and renewable
- Yu, Yue,Chen, Yang,Huang, Wei,Wu, Wanqing,Jiang, Huanfeng
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p. 9479 - 9486
(2017/09/23)
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- 4,5,6,7-TETRAHYDRO-1 H-PYRAZOLO[4,3-C]PYRIDIN-3-AMINE COMPOUNDS AS CBP AND/OR EP300 INHIBITORS
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The present invention relates to compounds of formula (I) or formula (II): and to salts thereof, wherein R1-R4 of formula (I) and R1-R3 of formula (II) have any of the values defined herein, and compositions and uses thereof. The compounds are useful as inhibitors of CBP and/or EP300. Also included are pharmaceutical compositions comprising a compound of formula (I) of formula (II) or a pharmaceutically acceptable salt thereof, and methods of using such compounds and salts in the treatment of various CBP and/or EP300-mediated disorders.
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Page/Page column 501
(2016/06/14)
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- Palladium-Catalyzed One-Pot Synthesis of 5-(1-Arylvinyl)-1H-benzimidazoles: Overcoming the Limitation of Acetamide Partners
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A new one-pot palladium-catalyzed process between N-tosylhydrazones, N-(dihalophenyl)-imidates, and amines was designed. This reaction involves Barluenga cross-coupling and N-arylation followed by cyclization to produce functionalized benzimidazoles. Duri
- Naret, Timothée,Retailleau, Pascal,Bignon, Jér?me,Brion, Jean-Daniel,Alami, Mouad,Hamze, Abdallah
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supporting information
p. 1833 - 1847
(2016/06/09)
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- The microwave-assisted ortho-alkylation of azine N-oxides with N-tosylhydrazones catalyzed by copper(i) iodide
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A copper catalyzed regioselective cross-coupling of N-tosylhydrazones with azine N-oxides to yield ortho-alkylated products in moderate to good yields is reported. The reaction is facilitated by microwave, takes place without any ligand, and uses inexpensive copper(i) iodide as the catalyst.
- Jha, Abadh Kishor,Jain, Nidhi
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supporting information
p. 1831 - 1834
(2016/02/05)
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- Catalyst-free synthesis of spiropyrazolines from chalcones and cyclic ketone N -tosylhydrazones
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Treatment of cyclic ketone N-tosylhydrazones with chalcones in the presence of cesium carbonate at 110 °C affords spiropyrazolines with high selectivity and excellent yields. This protocol possesses many advantages such as readily available and stable sta
- Wu, Qin-Xi,Li, Hui-Jing,Wang, Hong-Shuang,Zhang, Zhen-Guo,Wang, Chen-Chao,Wu, Yan-Chao
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supporting information
p. 243 - 249
(2015/03/05)
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- Regioselective Synthesis of Vinyl Halides, Vinyl Sulfones, and Alkynes: A Tandem Intermolecular Nucleophilic and Electrophilic Vinylation of Tosylhydrazones
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A diazo species is trapped in an intermolecular fashion by two independent ion species in tandem at the carbene center to install an electrophile and a nucleophile on the same carbon. This metal-free concept, which is unprecedented, has been illustrated by regioselective synthesis of a variety of vinyl halides, vinyl sulfones, and alkyne derivatives. (Chemical Equation Presented).
- Ojha, Devi Prasan,Prabhu, Kandikere Ramaiah
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supporting information
p. 18 - 21
(2015/07/28)
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- Preparation of unsymmetrical ketones from tosylhydrazones and aromatic aldehydes via formyl C-H bond insertion
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Preparation of ketones by insertion of diazo compounds into the formyl C-H bond of an aldehyde is an attractive procedure, but use of structurally diverse diazo compounds is hampered by preparation and safety issues. A convenient procedure for the synthesis of unsymmetrical ketones from bench-stable tosylhydrazones and aryl aldehydes is reported. The procedure can be performed in one pot from the parent carbonyl compound and needs only a base, with no additional promoters being required.
- Allwood, Daniel M.,Blakemore, David C.,Ley, Steven V.
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supporting information
p. 3064 - 3067
(2014/06/23)
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- Formal carbon insertion of n-tosylhydrazone into B-B and B-Si bonds: Gem-diborylation and gem-silylborylation of sp3 carbon
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A convenient method is developed to synthesize 1,1-diboronates from the corresponding N-tosylhydrazones. This method is also applicable to synthesize 1-silyl-1-boron compounds. Meanwhile, derivatization and consecutive Pd-catalyzed cross-coupling reaction
- Li, Huan,Shangguan, Xianghang,Zhang, Zhikun,Huang, Shan,Zhang, Yan,Wang, Jianbo
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supporting information
p. 448 - 451
(2014/04/03)
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- Facile one-pot synthesis of N-alkylated benzimidazole and benzotriazole from carbonyl compounds
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An efficient one-pot N-alkylation of benzimidazole and benzotriazole from carbonyl compounds and tosylhydrazide has been accomplished via copper powder-catalyzed N - H bond insertion affording N-alkylated products in good yields. The reaction can tolerate a wide range of carbonyl compounds, such as aryl, alkyl, heterocyclic and α,β-unsaturated ketones, and aldehydes.
- Meng, Xu,Li, Xiaolong,Chen, Wenlin,Zhang, Yuanqing,Wang, Wen,Chen, Jinying,Song, Jinli,Feng, Huijie,Chen, Baohua
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p. 349 - 356
(2014/04/17)
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- An unprecedented approach to the Gabriel amine synthesis utilizing tosylhydrazones as alkylating agents
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A new and one-pot version of the Gabriel phthalimide amine synthesis utilizing carbonyl compounds as alkylating agents via their tosylhydrazone surrogates is disclosed. The alkylation involves copper catalysed carbene insertion into the N-H bond of phthalimide. Basically, the protocol also offers a powerful tool for deoxygenative hydroamination of carbonyl compounds.
- Yadav, Arvind K.,Yadav, Lal Dhar S.
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p. 34764 - 34767
(2014/11/08)
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- Reductive coupling reactions: A new strategy for C(sp3)-P bond formation
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The C(sp3)-P bond forming reaction utilizing N-tosylhydrazones as readily available alkylating reagents was developed, which provides a new opportunity for preparing phosphine oxide derivatives with moderate to good yields. This reductive coupling reaction is proposed to proceed through an insertion of copper carbene into P-H bond of H-phosphorus oxides. The salient features of the reaction are operational simplicity and functional-group tolerance.
- Chen, Zi-Sheng,Zhou, Zhao-Zhao,Hua, Hui-Liang,Duan, Xin-Hua,Luo, Jian-Yi,Wang, Jia,Zhou, Ping-Xin,Liang, Yong-Min
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supporting information
p. 1065 - 1068
(2013/02/25)
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- N-Alkylation of tosylhydrazones in the presence of triphenylphosphine
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An efficient N-alkylation reaction of tosylhydrazones was developed in the presence of triphenylphosphine; triphenylphosphine played a key role in the transformation. A range of N-alkylated tosylhydrazones were prepared in good to high yields.
- Kong, Yuanfang,Zhang, Wen,Tang, Meng,Wang, Haiming
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supporting information
p. 7487 - 7491
(2013/08/23)
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- Olefination of carbonyl compounds through reductive coupling of alkenylboronic acids and tosylhydrazones
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The partners decide: The C-C bond-forming reductive cross-coupling of alkenylboronic acids and tosylhydrazones takes place under mild reaction conditions without the need of a metal catalyst, thus giving rise to olefination-type products (see scheme). The position of the double bond in the product is determined by the structure of the coupling partners. Copyright
- Perez-Aguilar, M. Carmen,Valdes, Carlos
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supporting information; experimental part
p. 5953 - 5957
(2012/07/30)
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- Coupling of n-tosylhydrazones with terminal alkynes catalyzed by copper(i): Synthesis of trisubstituted allenes
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The easy way to allenes: An operationally simple reaction under mild conditions has led to the direct formation of trisubstituted allenes (see scheme; Ts=4-toluenesulfonyl). An unprecedented copper-carbene migratory insertion process seems to take place,
- Xiao, Qing,Xia, Ying,Li, Huan,Zhang, Yan,Wang, Jianbo
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supporting information; experimental part
p. 1114 - 1117
(2011/04/16)
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- The benzyne Fischer-indole reaction
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A new approach to the Fischer-indole synthesis is reported that uses the reactive intermediate benzyne. The addition of N-tosyl hydrazones to arynes, generated through fluoride activation of 2-(trimethylsilyl)phenyl triflate precursors, leads to efficient
- McAusland, Donald,Seo, Sangwon,Pintori, Didier G.,Finlayson, Jonathan,Greaney, Michael F.
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supporting information; experimental part
p. 3667 - 3669
(2011/09/16)
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- Solvent-free synthesis of hydrazones and their subsequent N-alkylation in a Ball-mill
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A large variety of Boc-, Bz-, Ts-, and Fmoc- protected hydrazones were prepared via condensation of an equimolar amount of carbonyl-compound and the corresponding hydrazine using a ball-mill. Hydrazones were always obtained in a quantitative yield and no solvents were used at any step. In a second step, we realized the first solvent-free N-allylation and N-benzylation of these hydrazones.
- Nun, Pierrick,Martin, Charlotte,Martinez, Jean,Lamaty, Frédéric
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supporting information; experimental part
p. 8187 - 8194
(2011/10/31)
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- Copper carbenoid mediated N-alkylation of imidazoles and its use in a novel synthesis of bifonazole
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1H-Imidazoles are readily N-alkylated by a Cu(acac)2 mediated reaction with α-diazocarbonyl compounds or with diazoalkanes generated in situ from the corresponding p-toluensulfonyl hydrazones. The antifungal agent bifonazole was prepared by the latter method. Graphical Abstract.
- Cuevas-Ya?ez, Erick,Serrano, Juan Manuel,Huerta, Gloria,Muchowski, Joseph M.,Cruz-Almanza, Raymundo
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p. 9391 - 9396
(2007/10/03)
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- Structure-activity relationships of xanthene carboxamides, novel CCR1 receptor antagonists
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The structure-activity relationships of xanthene carboxamide derivatives on the CCR1 receptor binding affinity and the functional antagonist activity were described. Previously, we reported a quaternarized xanthen-9-carboxamide 1 as a potent human CCR1 receptor antagonist that was derived from a xanthen-9-carboxamide lead 2a. Further derivatization of 2a focusing on installing an additional substituent into the xanthene ring resulted in the identification of 2b-1 with IC50 values of 1.8 nM and 13 nM in the binding assay using human CCR1 receptors transfected CHO cells and in the functional assay using U937 cells expressing human CCR1 receptors, respectively.
- Naya, Akira,Ishikawa, Makoto,Matsuda, Kenji,Ohwaki, Kenji,Saeki, Toshihiko,Noguchi, Kazuhito,Ohtake, Norikazu
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p. 875 - 884
(2007/10/03)
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- Tetraethylammonium bromide catalysed phase transfer reaction of potassium superoxide with hydrazones and tosylhydrazones
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A variety of hydrazones and tosylhydrazones of carbonyl compounds have been investigated under the mild reaction conditions of potassium superoxide and tetraethylammonium bromide in dry dimethylformamide. As a result, hydrazones are generally transformed to their corresponding azines whereas tosylhydrazones undergo facile fragmentation to give the olefinic products in fairly good yields. The study highlights the use of tetraethylammonium bromide as an efficient and inexpensive catalyst for superoxide studies.
- Kumar,Singh
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p. 579 - 583
(2007/10/03)
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- Tosylhydrazines by the Reduction of Tosylhydrazones with Triethylsilane in Trifluoroacetic Acid
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Tosylhydrazines were easily prepared by the reduction of tosylhydrazones with triethylsilane in the presence of trifluoroacetic acid.
- Wu, Pei-Lin,Peng, Shao-Yu,Magrath, Joe
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p. 249 - 252
(2007/10/03)
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- An Extremely Efficient Way to Prepare Conjugated Carbonyl Compounds from Terminal Alkenes via the Reactions of Ozonides, Triethylamine and Stable Phosphorus Ylides
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Ozonides derived from mono- and 1,1-di-substituted olefins reacted with triethylamine in the presence of nucleophiles, such as phosphorus ylide or phosphonoacetate to give conjugated carbonyl compounds almost instantaneously in excellent yields.These transformations were accelerated by the by-product (i.e. thermal energy and ammonium formate) generated in the reaction.
- Hon, Yung-Son,Lu, Ling
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p. 7937 - 7942
(2007/10/02)
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- Generation and Solution-phase Behaviour of Some 2-Halogeno-1,3-ring-fused Cyclopropenes
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The title cyclopropenes 2b are readily formed by reaction of ring-fused β-silylated-gem-dihalogenocyclopropanes of the general type 1b with tetrabutylammonium fluoride in tetrahydrofuran solution.Those halogenocyclopropenes 2b which are fused to a seven-
- Banwell, Martin G.,Corbett, Madelaine,Gulbis, Jacqueline,Mackay, Maureen F.,Reum, Monica E.
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p. 945 - 964
(2007/10/02)
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- Reaction of Substituted Hydrazones with Thionyl Chloride and Sulfuryl Chloride
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Treatment of acetylhydrazones 2, ethoxycarbonylhydrazones 3, p-tolylsulfonylhydrazones 4 or semicarbazones 5 with thionyl chloride leads to the 1,2,3-thiadiazoles 6a-o.Sulfuryl chloride on the other hand accomplishes the transfer of chlorine without incorporating a sulfur atom.The new synthesized 1,2,3-thiadiazoles 6g-o are characterized in detail by spectroscopic methods.
- Meier, Herbert,Trickes, Georg,Laping, Elisabeth,Merkle, Ursula
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p. 183 - 192
(2007/10/02)
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