- Polysubstituted Indole Synthesis via Palladium/Norbornene Cooperative Catalysis of Oxime Esters
-
Polysubstituted indoles are prevalent in pharmaceuticals, agrochemicals, and organic materials. Presented herein is the fact that polyfunctionalized indoles can be efficiently constructed from easily accessible oxime esters and aryl iodides, involving a palladium/norbornene synergistic synthesis. The reaction is enabled by a unique class of electrophiles in palladium/norbornene cooperative catalysis, which are oxime esters derived from simple ketone. The broad substrate scope and high functional group tolerance could make this method attractive for the synthesis of polysubstituted indoles.
- Liu, Jiechun,Lin, Haojiang,Jiang, Huanfeng,Huang, Liangbin
-
supporting information
p. 484 - 489
(2022/01/20)
-
- Selective Cross-Dehydrogenative C(sp3)-H Arylation with Arenes
-
Selective C(sp3)-C(sp2) bond construction is of central interest in chemical synthesis. Despite the success of classic cross-coupling reactions, the cross-dehydrogenative coupling between inert C(sp3)-H and C(sp2)-H bonds represents an attractive alternative toward new C(sp3)-C(sp2) bonds. Herein, we establish a selective inter-and intramolecular C(sp3)-H arylation of alcohols with nondirected arenes that thereby provides a general pathway to access a wide range of β-arylated alcohols, including tetrahydronaphthalen-2-ols and benzopyran-3-ols, with high to excellent chemo-and regioselectivity.
- Hao, Hong-Yan,Mao, Yang-Jie,Xu, Zhen-Yuan,Lou, Shao-Jie,Xu, Dan-Qian
-
supporting information
p. 2396 - 2402
(2020/03/13)
-
- RhIII-Catalyzed Synthesis of Highly Substituted 2-Pyridones using Fluorinated Diazomalonate
-
A RhIII-catalyzed strategy was developed for the rapid construction of highly substituted 2-pyridone scaffolds using α,β-unsaturated oximes and fluorinated diazomalonate. The reaction proceeds through direct, site-selective alkylation based on migratory insertion and subsequent cyclocondensation. A wide substrate scope with different functional groups was explored. The requirement of fluorinated diazomalonate was explored for this transformation. The developed methodology was further extended with the synthesis of the bioactive compound.
- Das, Debapratim,Sahoo, Gopal,Biswas, Aniruddha,Samanta, Rajarshi
-
supporting information
p. 360 - 364
(2020/01/25)
-
- Silica gel-mediated self-aldol reactions of highly volatile aldehydes under organic solvent-free conditions without reflux condenser
-
Silica gel-mediated self-aldol reactions were catalyzed by piperidine to give the corresponding α,β-conjugated aldehydes in good yields. The aldol reactions of 4-nitro-, 4-trifluoromethyl-, and 4-chlorobenzaldehydes with acetone afforded the corresponding aldol products. Highly volatile aldehydes and acetone could be employed even without a reflux condenser for these reactions. Silica gel could be recycled five times without any significant decrease of the yields of the products.
- Tanemura, Kiyoshi
-
p. 1924 - 1928
(2019/06/24)
-
- Discovery of novel 5-methyl-1H-pyrazole derivatives as potential antiprostate cancer agents: Design, synthesis, molecular modeling, and biological evaluation
-
Androgen receptor (AR) signaling functions as a core driving force for the progression of prostate cancer (PCa), and AR has been proved to be an effective therapeutic target even for castration-resistant prostate cancer (CRPC). Herein, structural modification via a fragments splicing strategy was performed based on two lead compounds T3 and 10e, leading to the discovery of a series of 5-methyl-1H-pyrazole derivatives. AR reporter gene assay revealed compounds A13 and A14 as potent AR antagonists. Some of the compounds in this series inhibited growth of PCa LNCaP cells more efficiently than enzalutamide. A13 and A14 also showed improved metabolic stability compared with 10e in human liver microsomes.
- Zhang, Daoguang,Asnake, Solomon,Zhang, Jingya,Olsson, Per-Erik,Zhao, Guisen
-
p. 1113 - 1124
(2018/03/05)
-
- Rh(III)-Catalyzed Enaminone-Directed Alkenyl C-H Activation for the Synthesis of Salicylaldehydes
-
A Rh(III)-catalyzed enaminone-directed alkenyl C-H coupling with alkynes for the synthesis of salicylaldehyde derivatives is reported. This represents a unique example of benzene ring framework formation through a transition-metal-catalyzed, directed C-H activation strategy. The two incorporated reactive functionalities, aldehyde and hydroxy groups, provide convenient synthetic handles for further structural elaboration.
- Qi, Bing,Guo, Shan,Zhang, Wenjing,Yu, Xiaolong,Song, Chao,Zhu, Jin
-
supporting information
p. 3996 - 3999
(2018/07/15)
-
- Gram-scale preparation of dialkylideneacetones through Ca(OH)2-catalyzed Claisen-Schmidt condensation in dilute aqueous EtOH
-
A synthetic method of dialkylideneacetones has been developed. Compared with known protocols, the method employed catalytic Ca(OH)2 as the cheap, mild base catalyst and dilute aqueous EtOH (20%, v/v) as the green and safe solvent. The procedure was easily operated: In most cases, the product could be isolated by a simple filtration, and purified by washing with water. This paper provided experimental details of the reactions, which could be applied in gram-scale synthesis and should be a very reliable and practical protocol to prepare these useful compounds in laboratory and at the industrial level.
- Zhang, Hao,Han, Mengting,Yang, Chenggen,Yu, Lei,Xu, Qing
-
-
- Diastereoselective synthesis of β-amino ketone and acid derivatives by palladium-catalyzed conjugate addition
-
The first diastereoselective synthesis of β-amino ketone and β-amino acid derivatives by palladium-catalyzed conjugate addition of arylboronic acids to chiral β-enamino ketones and β-enamino esters is reported. The catalytic system employing (S)-4-(tert-butyl)oxazolidin-2-one as the chiral auxiliary in water under an air atmosphere provides β-amino ketone and β-amino acid derivatives in high yields with excellent diastereoselectivity.
- Zhi, Wubin,Li, Jingya,Zou, Dapeng,Wu, Yangjie,Wu, Yusheng
-
supporting information
p. 2736 - 2740
(2018/06/25)
-
- A method of preparing alpha,beta-unsaturated ketones
-
The invention relates to a method of preparing alpha,beta-unsaturated ketones. The method is characterized by comprising steps of (1) adding a copper catalyst and an alkali into a reaction tube, adding a liquid mixture of a solvent and reactants which are a beta-hydroxy ketone and an aromatic aldehyde under nitrogen protection into the reaction tube and reacting the mixture; (2) performing filtration, extraction, drying, and low-pressure solvent removing after the reaction is finished to obtain an alpha,beta-unsaturated ketone crude product; and (3) performing separation and purification to obtain an alpha,beta-unsaturated ketone product. A copper enolate is generated in situ through a retrograde aldol condensation reaction and is further subjected to aldol condensation with the aromatic aldehyde to obtain the final product. The beta-hydroxy ketone and the aromatic aldehyde are injected through injectors under nitrogen protection, and the reaction is performed under stirring in an oil bath pot having a temperature of 25-120 DEG C for 3-8 h. The method has characteristics of mild conditions, simple operation, easily available raw materials, and environment protection and is hopped to be widely applied in the fine chemical synthesis fields such as medicine intermediates, perfume and pesticides.
- -
-
Paragraph 0044; 0045; 0046; 0047; 0048
(2017/07/15)
-
- Application of Deep Eutectic Solvents in Promiscuous Lipase-Catalysed Aldol Reactions
-
The application of deep eutectic solvents has been demonstrated for the first time in promiscuous lipase-catalysed aldol reactions. The model reaction between 4-nitrobenzaldehyde and acetone was examined in depth, with excellent compatibility being found between porcine pancreas lipase and choline chloride/glycerol mixtures for the formation of the aldol product in high yields. The system was compatible with a series of aromatic aldehydes and ketones including acetone, cyclopentanone and cyclohexanone. In some cases, the corresponding α,β-unsaturated carbonyl compounds were found as minor products. Control experiments demonstrate that the enzymatic preparation was also responsible for a collateral dehydration reaction once the aldol product is formed. Deep eutectic solvents are used for the first time in promiscuous lipase-catalysed aldol reactions. The reaction between substituted benzaldehydes and aliphatic ketones has excellent compatibility with porcine pancreas lipase (PPL) and choline chloride/glycerol mixtures and gives the aldol product in high yields. PPL was also responsible for a collateral dehydration reaction.
- González-Martínez, Daniel,Gotor, Vicente,Gotor-Fernández, Vicente
-
supporting information
p. 1513 - 1519
(2016/04/05)
-
- Discovery of New Monocarbonyl Ligustrazine-Curcumin Hybrids for Intervention of Drug-Sensitive and Drug-Resistant Lung Cancer
-
The elevation of oxidative stress preferentially in cancer cells by inhibiting thioredoxin reductase (TrxR) and/or enhancing reactive oxygen species (ROS) production has emerged as an effective strategy for selectively targeting cancer cells. In this study, we designed and synthesized 21 ligustrazine-curcumin hybrids (10a-u). Biological evaluation indicated that the most active compound 10d significantly inhibited the proliferation of drug-sensitive (A549, SPC-A-1, LTEP-G-2) and drug-resistant (A549/DDP) lung cancer cells but had little effect on nontumor lung epithelial-like cells (HBE). Furthermore, 10d suppressed the TrxR/Trx system and promoted intracellular ROS accumulation and cancer cell apoptosis. Additionally, 10d inhibited the NF-κB, AKT, and ERK signaling, P-gp-mediated efflux of rhodamine 123, P-gp ATPase activity, and P-gp expression in A549/DDP cells. Finally, 10d repressed the growth of implanted human drug-resistant lung cancer in mice. Together, 10d acts a novel TrxR inhibitor and may be a promising candidate for intervention of lung cancer.
- Ai, Yong,Zhu, Bin,Ren, Caiping,Kang, Fenghua,Li, Jinlong,Huang, Zhangjian,Lai, Yisheng,Peng, Sixun,Ding, Ke,Tian, Jide,Zhang, Yihua
-
p. 1747 - 1760
(2016/03/25)
-
- Enzyme-catalyzed domino reaction: Efficient construction of spirocyclic oxindole skeleton using porcine pepsin
-
Pepsin from porcine gastric mucosa was used as a sustainable and environmentally friendly biocatalyst in the domino Knoevenagel/Michael/Michael reaction for the synthesis of spirooxindole derivatives in methanol. A wide range of isatins and α,β-unsaturated ketones reacting with malononitrile provided the corresponding products in yields of up to 99% with diastereoselectivities of up to >99:1 dr. This pepsin-catalyzed domino reaction provided a novel case of enzyme catalytic promiscuity.
- He, Yan-Hong,He, Tao,Guo, Jun-Tao,Li, Rui,Xiang, Yang,Yang, Da-Cheng,Guan, Zhi
-
p. 2239 - 2248
(2016/04/26)
-
- Synthesis and neuroprotective evaluation of (E)-3,4-dihydroxystyryl p-substituted-phenethyl ketone derivatives against inflammatory and oxidative injury
-
(E)-3,4-dihydroxystyryl p-substituted-phenethyl ketones and their 3,4-diacetylated derivatives were synthesized and examined their neuroprotective activities to further study the effect of p-substituents on the aromatic ring. The results revealed that steric hindrance effect of p-substituents has impact on neuroprotective activities against inflammatory and oxidative injury. Introduction of the bulkier groups are more beneficial to improve the neuroprotective activities than smaller groups. Compounds (4–5h, 4–5i and 4–5e) with p-substituted trifluoromethyl, isopropyl and t-butyl groups exhibited the best effects among all the target compounds.
- Cheng, Can,Ning, Xianling,Luo, Yongming,Tian, Chao,Wang, Xiaowei,Guo, Ying,Liu, Junyi,Zhang, Zhili
-
p. 1678 - 1685
(2016/07/30)
-
- Method for preparing alpha and beta-unsaturated ketone
-
The invention provides a method for preparing alpha and beta-unsaturated ketone. The method includes that L-proline is used as a catalyst, secondary amine is used as a cocatalyst, and the alpha and beta-unsaturated ketone can be directly synthesized in alcohol or ketone solution by means of aldol condensation under neutral conditions at one step. Compared with the traditional method, the method has the advantages that raw materials are easily available, the method is low in cost and is environmental friendly, reaction conditions are mild, solvents are clean and environmental friendly, equipment can be protected against corrosion under the neutral conditions, the catalyst is high in acid resistance, and the method is applicable to industrial production.
- -
-
Paragraph 0012; 0013; 0034; 0035; 0036; 0040; 0041
(2016/10/31)
-
- Synthesis of α-Tertiary Amine Derivatives by Intermolecular Hydroamination of Unfunctionalized Alkenes with Sulfamates under Trifluoromethanesulfonic Acid Catalysis
-
An efficient and mild trifluoromethanesulfonic acid-catalyzed hydroamination of unfunctionalized alkenes to afford α-tertiary amine derivatives at temperatures as low as room temperature is reported. 2,2,2-Trifluoroethyl sulfamate was found to be the optimal nitrogen source because its good solubility in both organic solvents and water facilitated both conversion and purification. The reaction conditions were compatible with a variety of substrate functional groups and afforded moderate to good yields. The desired amine compounds could be obtained easily by means of a mild, one-pot, redox-neutral deprotection procedure. Caryolane amine was synthesized with excellent chemo- and regioselectivities by means of a cascade hydroamination reaction of β-caryophyllene.
- Fei, Jun,Wang, Zhen,Cai, Zheren,Sun, Hao,Cheng, Xu
-
supporting information
p. 4063 - 4068
(2016/01/25)
-
- Synthesis of Polysubstituted Pyridines via a One-Pot Metal-Free Strategy
-
An efficient strategy for the one-pot synthesis of polysubstituted pyridines via a cascade reaction from aldehydes, phosphorus ylides, and propargyl azide is reported. The reaction sequence involves a Wittig reaction, a Staudinger reaction, an aza-Wittig reaction, a 6π-3-azatriene electrocyclization, and a 1,3-H shift. This protocol provides quick access to the polysubstituted pyridines from readily available substrates in good to excellent yields.
- Wei, Hongbo,Li, Yun,Xiao, Ke,Cheng, Bin,Wang, Huifei,Hu, Lin,Zhai, Hongbin
-
supporting information
p. 5974 - 5977
(2016/01/09)
-
- Wacker-type oxidation and dehydrogenation of terminal olefins using molecular oxygen as the sole oxidant without adding ligand
-
An efficient and economical palladium-catalyzed oxidation system has been identified. The oxidation system, characterized by not adding ligand and using molecular oxygen as the sole oxidant, can realize the Tsuji-Wacker oxidation of terminal olefins and especially styrenes to methyl ketones; in addition, this system can achieve tandem Wacker oxidation-dehydrogenation of terminal olefins to α,β-unsaturated ketones.
- Wang, Yu-Fei,Gao, Ya-Ru,Mao, Shuai,Zhang, Yan-Lei,Guo, Dong-Dong,Yan, Zhao-Lei,Guo, Shi-Huan,Wang, Yong-Qiang
-
supporting information
p. 1610 - 1613
(2014/04/17)
-
- Enantioselective [4 + 2] cycloaddition of cyclic N-sulfimines and acyclic enones or ynones: A concise route to sulfamidate-fused 2,6-disubstituted piperidin-4-ones
-
A concise route to valuable sulfamate-fused 2,6-disubstituted piperidin-4-ones or 2,3-dihydropyridin-4(1H)-ones in good yield with high diastereo- and enantioselectivity is presented. The combination of chiral primary amine and o-fluorobenzoic acid efficiently promoted an asymmetric [4 + 2] cycloaddition reaction of N-sulfonylimines and enones or ynones. The cycloaddition reaction between cyclic N-sulfonylimines and ynones is first reported.
- Liu, Yong,Kang, Tai-Ran,Liu, Quan-Zhong,Chen, Lian-Mei,Wang, Ya-Chuan,Liu, Jie,Xie, Yong-Mei,Yang, Jin-Liang,He, Long
-
p. 6090 - 6093
(2014/01/06)
-
- Synthesis of β-sulfanyl ketones via a tandem rearrangement-conjugate addition reaction catalyzed by a Re(V)-oxo complex
-
A method for synthesizing β-sulfanyl ketones via a tandem rearrangement and conjugate addition reaction has been developed. This methodology provides access to a range of β-sulfanyl ketones through the rearrangement of propargyl alcohols to the corresponding enones followed by the conjugate addition of unactivated thiols. The one-pot, tandem transformation is catalyzed by ReOCl3(OPPh3)(S(CH3)2) affording aryl and alkyl β-sulfanyl ketones in good to excellent yield.
- Garst, Alyson E.,Badiceanu, Alexandra D.,Nolin, Kristine A.
-
supporting information
p. 459 - 461
(2013/02/23)
-
- Synthesis of acid-base bifunctional mesoporous materials by oxidation and thermolysis
-
A novel and efficient method has been developed for the synthesis of acid-base bifunctional catalyst SO3H-MCM-41-NH2. This method was achieved by co-condensation of tetraethylorthosilicate (TEOS), 3-mercaptopropyltrimethoxysilane (MPTMS) and (3-triethoxysilylpropyl) carbamicacid-1-methylcyclohexylester (3TAME) in the presence of cetyltrimethylammonium bromide (CTAB), followed by oxidation and then thermolysis to generate acidic site and basic site. X-ray diffraction (XRD) and transmission electron micrographs (TEM) show that the resultant materials keep mesoporous structure. Thermogravimetric analysis (TGA), X-ray photoelectron spectra (XPS), back titration, solid-state 13C CP/MAS NMR and solid-state 29Si MAS NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The bifunctional sample (SO 3H-MCM-41-NH2) containing amine and sulfonic acids exhibits excellent acid-basic properties, which make it possess high activity in aldol condensation reaction between acetone and various aldehydes.
- Yu, Xiaofang,Zou, Yongcun,Wu, Shujie,Liu, Heng,Guan, Jingqi,Kan, Qiubin
-
experimental part
p. 951 - 957
(2011/06/27)
-
- Synthesis and biological activity of novel tiliroside derivants
-
A series of new tiliroside derivatives were synthesized and characterized by analytical 1H NMR, 13C NMR and mass spectrometry. All of the compounds were evaluated for anti-diabetic properties in vitro using HepG2 cells. Compounds 3c, 3d, and 3i-l caused significant enhancements in glucose consumption by insulin-resistant HepG2 cells compared with control cells and cells that were exposed to metformin (an anti-diabetic drug). Moreover, compound 3l significantly activated adenosine 5′-monophosphate-activated protein kinase activity and reduced acetyl-CoA carboxylase activity. Thus, the tiliroside derivative 3l offers potential to be developed as a new approach for treating type II diabetes.
- Qin, Nan,Li, Chun-Bao,Jin, Mei-Na,Shi, Li-Huan,Duan, Hong-Quan,Niu, Wen-Yan
-
scheme or table
p. 5189 - 5195
(2011/11/14)
-
- A simple and efficient synthesis of pyrazoles in water
-
A simple, highly efficient, and environmentally friendly method for the synthesis of substituted 1H-pyrazoles by one-pot condensation reaction of α,β-unsaturated carbonyl compounds with tosyl hydrazide in water was developed. The reaction system exhibited tolerance with various functional groups, Aromatic moiety with both electron-rich and electron-deficient substituents could give desired products in good to excellent yields.
- Wen, Jun,Fu, Yun,Zhang, Ruo-Yi,Zhang, Ji,Chen, Shan-Yong,Yu, Xiao-Qi
-
supporting information; experimental part
p. 9618 - 9621
(2011/12/14)
-
- Dehydrozingerone and its analogues as inhibitors of nonenzymatic lipid peroxidation
-
The antioxidant property of dehydrozingerone and its analogs were investigated in the ferric-ascorbate induced lipid peroxidation model in rat brain homogenate. All the non phenolic compounds were either inactive or less active, while phenolic compounds w
- Rajakumar,Rao
-
p. 516 - 519
(2007/10/02)
-
- Synthesis and Antimalarial Properties of 1-Imino Derivatives of 7-Chloro-3-substituted-3,4-dihydro-1,9(2H,10H)-acridinediones and Related Structures
-
To improve upon the activity and properties of the 3-aryl-7-chloro-3,4-dihydro-1,9(2H,10H)-acridinediones, a variety of 1-imino derivatives (3) were prepared and shown to be highly active antimalarial agents in both rodents and primates.Among structural modifications prepared, including N10-alkyl and C2-substituted analogs, removal of the C9 oxygen, and introduction of an imino side chain at C9, the imines of the N10-H acridinediones were the most active compounds obtained.The imino derivative of7-chloro-3-(2,4-dichlorophenyl)-3,4-dihydro-1,9(2H,10H)-acridinedione (9aa) proved to be highly active in advanced studies in primates.
- Kesten, Stephen J.,Degnan, Margaret J.,Hung, Jocelyn,McNamara, Dennis J.,Ortwine, Daniel F.,et al.
-
p. 3429 - 3447
(2007/10/02)
-