- Nucleophilic fluoroalkylation of terminal vinyl triflones with SO2CF3 as a removable activating group
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Terminal vinyl triflones served as excellent Michael addition acceptors which readily reacted with difluoromethylene phosphabetaine and di- or mono-fluoroalkyl bromides to afford compounds containing CF2 or CF groups. This fluoroalkylation is c
- Tian, Ping-ping,Xiao, Hong-qing,Wang, Lu,Yu, Yingxin,Huang, Yangen
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Read Online
- Traceless sulfone linker cleavage triggered by ozonolysis: solid-phase synthesis of diverse α-β-unsaturated carbonyl compounds
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The highly efficient and convenient protocol to prepare diverse α,β-unsaturated aldehydes, ketones, and acids via the parallel solid-phase synthesis is developed. The key sulfone linker cleavage strategy is performed by ozonolysis to generate a carbonyl moiety followed by base-mediated polymer-bound sulfinate elimination to release our desired molecules from the resin. All α,β-unsaturated carbonyl compounds are prepared in good purities and yields without further purification.
- Chang, Yi-Fan,Jiang, Yi-Rui,Cheng, Wei-Chieh
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Read Online
- Fluorinated Sulfinates as Source of Alkyl Radicals in the Photo-Enantiocontrolled β-Functionalization of Enals
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The generation of sulfonyl radicals has long been known as a flexible strategy in a wide range of different sulfonylative transformations. Meanwhile their use in alkylation processes has been somehow limited due to their inherent difficulty in evolving to less-stable radicals after sulfur dioxide extrusion. Herein we report a convenient strategy that involves gem-difluorinated sulfinates as an “upgrading-mask”, allowing these precursors to decompose into their corresponding alkyl radicals. The electron–donor character of sulfinates in the formation of an electron donor–acceptor (EDA) complex with transient iminium ions is displayed, achieving the first example of a stereocontrolled light-driven insertion of gem-difluoro derivatives into unsaturated aldehydes. This methodology is compatible with flow conditions, maintaining identical levels of enantiocontrol.
- Alemán, José,Rodríguez, Ricardo I.,Sicignano, Marina
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supporting information
(2022/01/22)
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- An efficient Pd@Pro-GO heterogeneous catalyst for the α, β-dehydrogenation of saturated aldehyde and ketones
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An Efficient Pd@Pro-GO heterogeneous catalyst was developed that can promote the α, β-dehydrogenation of saturated aldehyde and ketones in the yield of 73% ? 92% at mild conditions without extra oxidants and additives. Pd@Pro-GO heterogeneous catalyst was synthesized via two steps: firstly, the Pro-GO was obtained by the esterification reaction between graphene oxide (GO) and N-(tert-Butoxycarbonyl)-L-proline (Boc-Pro-OH), followed by removing the protection group tert-Butoxycarbonyl (Boc), which endowed the proline-functionalized GO with both the lewis acid site (COOH) and the bronsted base site (NH), besides, the pyrrolidine of proline also can form imine with aldehydes to activate these substrates; Second, palladium was dispersed on the proline-functionalized GO (Pro-GO) to obtained heterogeneous catalyst Pd@Pro-GO. Mechanistic studies have shown that the Pd@Pro-GO-catalyzed α,β-dehydrogenation of saturated aldehyde and ketones was realized by an improved heterogeneously catalyzed Saegusa oxidation reaction. Based on the obove characteristics, the Pd@Pro-GO will be widely used in the transition metal catalytic field.
- Pan, Gao-Fei,Wang, Zhe,Chang, Yi-Yuan,Hao, Yue,Wang, Yi-Chen,Xing, Rui-Guang
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supporting information
(2021/12/30)
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- Iron-Catalyzed ?±,?-Dehydrogenation of Carbonyl Compounds
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An iron-catalyzed α,β-dehydrogenation of carbonyl compounds was developed. A broad spectrum of carbonyls or analogues, such as aldehyde, ketone, lactone, lactam, amine, and alcohol, could be converted to their α,β-unsaturated counterparts in a simple one-step reaction with high yields.
- Zhang, Xiao-Wei,Jiang, Guo-Qing,Lei, Shu-Hui,Shan, Xiang-Huan,Qu, Jian-Ping,Kang, Yan-Biao
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supporting information
p. 1611 - 1615
(2021/03/03)
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- Method for preparing olefine aldehyde by catalyzing terminal alkyne or terminal conjugated eneyne and diphosphine ligand used in method
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The invention discloses a method for preparing olefine aldehyde by catalyzing terminal alkyne or terminal conjugated eneyne and a diphosphine ligand used in the method. According to the invention, indole-substituted phosphoramidite diphosphine ligand which is stable in air and insensitive to light is synthesized by utilizing a continuous one-pot method, and the indole-substituted phosphoramidite diphosphine ligand and a rhodium catalyst are used for jointly catalyzing to successfully achieve a hydroformylation reaction of aromatic terminal alkyne and terminal conjugated eneyne under the condition of synthesis gas for the first time, so that an olefine aldehyde structure compound can be rapidly and massively prepared, and particularly, a polyolefine aldehyde structure compound which is more difficult to synthesize in the prior art can be easily prepared and synthesized, and a novel method is provided for synthesis and modification of drug molecules, intermediates and chemical products.
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Paragraph 0126-0131
(2021/05/29)
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- Selective Rhodium-Catalyzed Hydroformylation of Terminal Arylalkynes and Conjugated Enynes to (Poly)enals Enabled by a π-Acceptor Biphosphoramidite Ligand
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The hydroformylation of terminal arylalkynes and enynes offers a straightforward synthetic route to the valuable (poly)enals. However, the hydroformylation of terminal alkynes has remained a long-standing challenge. Herein, an efficient and selective Rh-catalyzed hydroformylation of terminal arylalkynes and conjugated enynes has been achieved by using a new stable biphosphoramidite ligand with strong π-acceptor capacity, which affords various important E-(poly)enals in good yields with excellent chemo- and regioselectivity at low temperatures and low syngas pressures.
- Zhao, Jiangui,Zheng, Xueli,Tao, Shaokun,Zhu, Yuxin,Yi, Jiwei,Tang, Songbai,Li, Ruixiang,Chen, Hua,Fu, Haiyan,Yuan, Maolin
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supporting information
p. 6067 - 6072
(2021/08/16)
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- Scalable Aerobic Oxidation of Alcohols Using Catalytic DDQ/HNO3
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A selective, practical, and scalable aerobic oxidation of alcohols is described that uses catalytic amounts of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and HNO3, with molecular oxygen serving as the terminal oxidant. The method was successfully applied to the oxidation of a wide range of benzylic, propargylic, and allylic alcohols, including two natural products, namely, carveol and podophyllotoxin. The conditions are also applicable to the selective oxidative deprotection of p-methoxybenzyl ethers.
- Arseniyadis, Stellios,Clavier, Louis,Copin, Chloé,Fournier, Jean,Giffard, Jean-Fran?ois,Jean, Alexandre,Katsina, Tania,Macedo Portela Da Silva, Nayane,Tamion, Rodolphe
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supporting information
p. 856 - 860
(2020/07/14)
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- Biocatalytic reduction of α,β-unsaturated carboxylic acids to allylic alcohols
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We have developed robust in vivo and in vitro biocatalytic systems that enable reduction of α,β-unsaturated carboxylic acids to allylic alcohols and their saturated analogues. These compounds are prevalent scaffolds in many industrial chemicals and pharmaceuticals. A substrate profiling study of a carboxylic acid reductase (CAR) investigating unexplored substrate space, such as benzo-fused (hetero)aromatic carboxylic acids and α,β-unsaturated carboxylic acids, revealed broad substrate tolerance and provided information on the reactivity patterns of these substrates. E. coli cells expressing a heterologous CAR were employed as a multi-step hydrogenation catalyst to convert a variety of α,β-unsaturated carboxylic acids to the corresponding saturated primary alcohols, affording up to >99percent conversion. This was supported by the broad substrate scope of E. coli endogenous alcohol dehydrogenase (ADH), as well as the unexpected CC bond reducing activity of E. coli cells. In addition, a broad range of benzofused (hetero)aromatic carboxylic acids were converted to the corresponding primary alcohols by the recombinant E. coli cells. An alternative one-pot in vitro two-enzyme system, consisting of CAR and glucose dehydrogenase (GDH), demonstrates promiscuous carbonyl reductase activity of GDH towards a wide range of unsaturated aldehydes. Hence, coupling CAR with a GDH-driven NADP(H) recycling system provides access to a variety of (hetero)aromatic primary alcohols and allylic alcohols from the parent carboxylates, in up to >99percent conversion. To demonstrate the applicability of these systems in preparative synthesis, we performed 100 mg scale biotransformations for the preparation of indole-3-aldehyde and 3-(naphthalen-1-yl)propan-1-ol using the whole-cell system, and cinnamyl alcohol using the in vitro system, affording up to 85percent isolated yield.
- Aleku, Godwin A.,Leys, David,Roberts, George W.
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p. 3927 - 3939
(2020/07/09)
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- Boosting multiple photo-assisted and temperature controlled reactions with a single redox-switchable catalyst: Solvents as internal substrates and reducing agent
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An alternative and economically viable process for the synthesis of β-aryl enals, enones and the aryl amines has been developed by partial oxidation of ethanol, isopropanol and N, N-dimethyl formamide (DMF). The formation of β-aryl enals, enones and the aryl amines was catalyzed by a mixed metal oxides layer of cobalt and chromium supported on halloysite nanotubes, designated as CoCr2O4-HNT. The C[sbnd]C and C[sbnd]N bond formation reactions were found to be influenced by temperature and the nature of base. The condensation of aldehyde with in situ generated acetaldehyde by ethanol oxidation forming β-aryl enals occurred selectively at 120 °C. The partial oxidation of isopropanol to acetone and its condensation with aldehydes forming β-aryl enones occurred at room temperature. Increase in temperature caused the liberation of hydrogen gas from isopropanol and allowed the reversible reduction of aldehydes to alcohols. Increase in temperature in isopropanol and increase in base concentration in ethanol causes the selective reduction of aldehydes to alcohols. Besides being active for the Claisen-Schmidt type of reactions and the aryl halides amination process, the synthesized catalyst was also found to be highly active for the photocatalytic oxidation of benzyl alcohols in absence of any external oxidizing agent. The positive holes (h+) generated at the Co(II) site as evident from EPR analysis was considered to be responsible for high photocatalytic activity of the material reducing the recombination rate of holes and electrons (e?). Density Functional Theory calculations were performed to understand the mechanism of ethanol oxidation to acetaldehyde.
- Bania, Kusum K.,Baruah, Manash J.,Bhattacharyya, Pradip K.,Das, Biraj,Karunakar, Galla V.,Roy, Subhasish,Saikia, Lakshi,Saikia, Pinku,Sharma, Mukesh
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p. 104 - 121
(2020/06/01)
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- Highly Regio- A nd Enantioselective Hydrogenation of Conjugated α-Substituted Dienoic Acids
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Highly regio- A nd enantioselective hydrogenation of conjugated α-substituted dienoic acids was realized for the first time using Trifer-Rh complex, providing a straightforward method for the synthesis of chiral α-substituted ?,?′-unsaturated acids. DFT calculations revealed N+H-O hydrogen bonding interaction is formed to stabilize the transition state and the coordination of 4,5-double bond to Rh(III) center would facilitate the reductive elimination process. This hydrogenation provided a gram-scale synthesis of the precursor of sacubitril.
- Liu, Xian,Liu, Song,Wang, Quanjun,Zhou, Gang,Yao, Lin,Ouyang, Qin,Jiang, Ru,Lan, Yu,Chen, Weiping
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supporting information
p. 3149 - 3154
(2020/04/09)
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- Pd-Au-Y as Efficient Catalyst for C-C Coupling Reactions, Benzylic C-H Bond Activation, and Oxidation of Ethanol for Synthesis of Cinnamaldehydes
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Pd-Au nanoalloy supported on zeolite-Y (Pd-Au-Y) matrix was found to be an effective catalyst for C-Cl bond activation and oxidative coupling of 2-naphthol, leading to the formation of various biaryl products and 1,1′-bi-2-naphthol, BINOL. The same catalyst was also highly efficient for selective oxidation of benzylic alcohols to benzaldehydes. Cinnamaldehydes were obtained directly from benzaldehydes by aldol condensation with acetaldehyde generated in situ by partial oxidation of ethanol in the presence of Pd-Au-Y catalyst at 120 °C under basic condition. The biaryl products were also obtained directly from benzylic alcohols in a one-pot system by reacting with phenylboronic acid. The formation of biaryls from benzylic alcohols was believed to occur via one-pot benzylic C-H and C-Cl bond activation. A high % yield of biaryls, BINOL, aldehydes, and cinnamaldehydes was obtained by performing different reactions using the single Pd-Au-Y catalyst. The strong interaction of chloro-benzylic alcohol was predominantly located at active gold species. X-ray photoelectron and diffuse reflectance spectroscopic studies revealed the strong interaction between Pd and Au particles. Electrochemical studies provided proper evidence for the individual role of the nanoparticles (NPs) in one-pot synthesis of biaryls from benzylic alcohols.
- Sharma, Mukesh,Das, Biraj,Baruah, Manash J.,Biswas, Subir,Roy, Subhasish,Hazarika, Anil,Bhargava, Suresh K.,Bania, Kusum K.
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p. 5860 - 5875
(2019/06/17)
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- Iron(III)/O2-Mediated Regioselective Oxidative Cleavage of 1-Arylbutadienes to Cinnamaldehydes
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A simple, efficient, and environmentally benevolent regioselective oxidative cleavage of 1-arylbutadienes to cinnamaldehydes mediated by iron(III) sulfate/O2 has been developed. The reaction offered good yields and excellent regioselectivity and showed good functional group tolerance (31 examples). The method is important, as few reports with limited substrate scope are available for such excellent oxidative cleavage of conjugated dienes.
- Bhowmik, Amit,Fernandes, Rodney A.
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p. 9203 - 9207
(2019/11/14)
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- Palladium-catalyzed hydroformylation of terminal arylacetylenes with glyoxylic acid
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A simple, practical and governable palladium-catalyzed hydroformylation of terminal arylacetylenes has been disclosed. The reaction proceeds under syngas-free conditions, using readily available glyoxylic acid as the formyl source, under mild conditions, giving rise to a broad range of α,β-unsaturated aldehydes.
- Liu, Yang,Cai, Liangzhen,Xu, Sheng,Pu, Weiwen,Tao, Xiaochun
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supporting information
p. 2166 - 2168
(2018/03/06)
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- Novel Staphyloxanthin Inhibitors with Improved Potency against Multidrug Resistant Staphylococcus aureus
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Diapophytoene desaturase (CrtN) is a potential novel target for intervening in the biosynthesis of the virulence factor staphyloxanthin. In this study, 38 1,4-benzodioxan-derived CrtN inhibitors were designed and synthesized to overwhelm the defects of leading compound 4a. Derivative 47 displayed superior pigment inhibitory activity, better hERG inhibitory properties and water solubility, and significantly sensitized MRSA strains to immune clearance in vitro. Notably, 47 displayed excellent efficacy against pigmented S. aureus Newman, Mu50 (vancomycin-intermediate MRSA, VISA), and NRS271 (linezolid-resistant MRSA, LRSA) comparable to that of linezolid and vancomycin in vivo.
- Ni, Shuaishuai,Li, Baoli,Chen, Feifei,Wei, Hanwen,Mao, Fei,Liu, Yifu,Xu, Yixiang,Qiu, Xiaoxi,Li, Xiaokang,Liu, Wenwen,Hu, Linghao,Ling, Dazheng,Wang, Manjiong,Zheng, Xinyu,Zhu, Jin,Lan, Lefu,Li, Jian
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supporting information
p. 233 - 237
(2018/03/21)
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- Palladium-Catalyzed Cascade Double C—N Bond Activation: A New Strategy for Aminomethylation of 1,3-Dienes with Aminals
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A new palladium-catalyzed selective aminomethylation of conjugated 1,3-dienes with aminals via double C—N bond activation is described. This simple method provides an effective and rapid approach for the synthesis of linear α,β-unsaturated allylic amines with perfect regioselectivity. Mechanistic studies disclosed that one palladium catalyst cleaved two distinct C—N bond to furnish a cascade double C—N bond activation, in which an allylic 1,3-diamine and allylic 1,2-diamine were initially formed as key intermediates through the palladium-catalyzed C—N bond activation of aminal and the α,β-unsaturated allylic amine was subsequently produced via palladium-catalyzed C—N bond activation of the allylic diamines.
- Qiao, Cuifang,Chen, Anrong,Gao, Bingjian,Liu, Yang,Huang, Hanmin
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supporting information
p. 929 - 933
(2018/09/22)
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- Modular synthesis of (E)-cinnamaldehydes directly from allylarenes via a metal-free DDQ-mediated oxidative process
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An efficient synthesis of (E)-cinnamaldehydes by a metal-free DDQ-mediated oxidative transformation of allylarenes was developed. The protocol provides a practical method to prepare diverse (E)-cinnamaldehydes with broad functional group tolerance in good to excellent yields, including easy access to natural products randainal and geranyloxy sinapyl aldehyde from plant extracts. Finally, the mechanism of a single-electron transfer process was proposed.
- Xu, Ting-Ting,Jiang, Tao-Shan,Han, Xiao-Lan,Xu, Yuan-Hong,Qiao, Jin-Ping
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p. 5350 - 5358
(2018/08/03)
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- Novel Inhibitors of Staphyloxanthin Virulence Factor in Comparison with Linezolid and Vancomycin versus Methicillin-Resistant, Linezolid-Resistant, and Vancomycin-Intermediate Staphylococcus aureus Infections in Vivo
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Our previous work (Wang et al. J. Med. Chem. 2016, 59, 4831-4848) revealed that effective benzocycloalkane-derived staphyloxanthin inhibitors against methicillin-resistant Staphylococcus aureus (S. aureus) infections were accompanied by poor water solubility and high hERG inhibition and dosages (preadministration). In this study, 92 chroman and coumaran derivatives as novel inhibitors have been addressed for overcoming deficiencies above. Derivatives 69 and 105 displayed excellent pigment inhibitory activities and low hERG inhibition, along with improvement of solubility by salt type selection. The broad and significantly potent antibacterial spectra of 69 and 105 were displayed first with normal administration in the livers and hearts in mice against pigmented S. aureus Newman, Mu50 (vancomycin-intermediate S. aureus), and NRS271 (linezolid-resistant S. aureus), compared with linezolid and vancomycin. In summary, both 69 and 105 have the potential to be developed as good antibacterial candidates targeting virulence factors.
- Ni, Shuaishuai,Wei, Hanwen,Li, Baoli,Chen, Feifei,Liu, Yifu,Chen, Wenhua,Xu, Yixiang,Qiu, Xiaoxia,Li, Xiaokang,Lu, Yanli,Liu, Wenwen,Hu, Linhao,Lin, Dazheng,Wang, Manjiong,Zheng, Xinyu,Mao, Fei,Zhu, Jin,Lan, Lefu,Li, Jian
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p. 8145 - 8159
(2017/10/18)
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- One-Pot Synthesis of (S)-Baclofen via Aldol Condensation of Acetaldehyde with Diphenylprolinol Silyl Ether Mediated Asymmetric Michael Reaction as a Key Step
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An efficient asymmetric total synthesis of (S)-baclofen was accomplished via a one-pot operation from commercially available materials using sequential reactions, such as aldol condensation of acetaldehyde, diphenylprolinol silyl ether mediated asymmetric Michael reaction of nitromethane, Kraus-Pinnick oxidation, and Raney Ni reduction. Highly enantioenriched baclofen was obtained in one pot with a good yield over four reactions.
- Hayashi, Yujiro,Sakamoto, Daisuke,Okamura, Daichi
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supporting information
p. 4 - 7
(2016/01/15)
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- FENDILINE DERIVATIVES AND METHODS OF USE THEREOF
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Disclosed herein are novel derivatives of fendiline, including compounds of the formula: wherein the variables are defined herein. Also provided are pharmaceutical compositions, kits and articles of manufacture comprising these derivative compounds. Methods and intermediates useful for making the derivatives, and methods of using the derivatives, for example, for the inhibition of K-Ras plasma membrane localization, and compositions thereof, including for the treatment of cancer, are also provided.
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Page/Page column 82; 83
(2014/03/25)
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- Synthesis of functionalized cinnamaldehyde derivatives by an oxidative heck reaction and their use as starting materials for preparation of Mycobacterium tuberculosis 1-deoxy-d-xylulose-5-phosphate reductoisomerase inhibitors
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Cinnamaldehyde derivatives were synthesized in good to excellent yields in one step by a mild and selective, base-free palladium(II)-catalyzed oxidative Heck reaction starting from acrolein and various arylboronic acids. Prepared α,β-unsaturated aldehydes were used for synthesis of novel α-aryl substituted fosmidomycin analogues, which were evaluated for their inhibition of Mycobacterium tuberculosis 1-deoxy-d-xylulose 5-phosphate reductoisomerase. IC50 values between 0.8 and 27.3 μM were measured. The best compound showed activity comparable to that of the most potent previously reported α-aryl substituted fosmidomycin-class inhibitor.
- Nordqvist, Anneli,Bjoerkelid, Christofer,Andaloussi, Mounir,Jansson, Anna M.,Mowbray, Sherry L.,Karlen, Anders,Larhed, Mats
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experimental part
p. 8986 - 8998
(2011/12/03)
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- Pd-catalyzed cascade Heck-Saegusa: Direct synthesis of enals from aryl iodides and allyl alcohol
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A new efficient Pd-catalyzed cascade Heck-Saegusa protocol for the synthesis of synthetically useful α,β-unsaturated aldehydes in high yields from readily available aryl iodides and allyl alcohol has been developed.
- Liu, Jie,Zhu, Jin,Jiang, Hualiang,Wang, Wei,Li, Jian
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supporting information; experimental part
p. 415 - 417
(2010/04/04)
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- Direct oxidation of β-aryl substituted aldehydes to α,β-unsaturated aldehydes promoted by an o-anisidine-Pd(OAc) 2 Co-catalyst
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An o-anisidine-Pd(OAc)2 catalytic system for the direct co-catalytic Saegusa oxidation of β-aryl substituted aldehydes to α,β-unsaturated aldehydes has been developed. The use of o-anisidine in place of (S)-diphenylprolinol made the process more simply and cost-effective. The process not only features the use of unmodified aldehydes rather than enol silyl ethers, but also gives moderate to good yields (44-72%).
- Liu, Jie,Zhu, Jin,Jiang, Hualiang,Wang, Wei,Li, Jian
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experimental part
p. 1712 - 1716
(2010/04/30)
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- An improved general method for palladium catalyzed alkenylations and alkynylations of aryl halides under microwave conditions
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Palladium catalyzed facile method for alkenylation and alkynylation of arylhalides in good to excellent yield under microwave condition is reported.
- Togninelli, Andrea,Gevariya, Harsukh,Alongi, Maddalena,Botta, Maurizio
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p. 4801 - 4803
(2008/02/05)
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- An efficient palladium-catalyzed synthesis of cinnamaldehydes from acrolein diethyl acetal and aryl iodides and bromides
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(Matrix presented) The reaction of aryl iodides and bromides with acrolein diethyl acetal in the presence of Pd(OAc)2, nBu 4NOAc, K2CO3, KCl, and DMF, at 90°C until the disappearance of the acetal followed by the addition of 2 N HCl to the crude reaction mixture, affords cinnamaldehydes in good to high yields. A variety of functional groups are tolerated in the aryl halides, including ether, aldehyde, ketone, ester, dialkylamino, nitrile, and nitro groups. The presence of substituents close to the oxidative addition site does not hamper the reaction.
- Battistuzzi, Gianfranco,Cacchi, Sandro,Fabrizi, Giancarlo
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p. 777 - 780
(2007/10/03)
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- One Pot Synthesis of p-Polyphenyls via the Intramolecular Cyclization of 3-Dimethylaminohex-5-en-1-ynes
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Para linked polyphenyls of various molecular weights are conveniently synthesized from p-bis(3-dimethylamino-1-propynyl)arenes and 1-aryl-2-propenyl bromides in moderate yields using a three step, one-pot procedure.
- Unroe, Marilyn R.,Reinhardt, Bruce A.
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p. 981 - 986
(2007/10/02)
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