- Catalytic Asymmetric Allylic Substitution with Copper(I) Homoenolates Generated from Cyclopropanols
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By using copper(I) homoenolates as nucleophiles, which are generated through the ring-opening of 1-substituted cyclopropane-1-ols, a catalytic asymmetric allylic substitution with allyl phosphates is achieved in high to excellent yields with high enantioselectivity. Both 1-substituted cyclopropane-1-ols and allylic phosphates enjoy broad substrate scopes. Remarkably, various functional groups, such as ether, ester, tosylate, imide, alcohol, nitro, and carbamate are well tolerated. Moreover, the present method is nicely extended to the asymmetric construction of quaternary carbon centers. Some control experiments argue against a radical-based reaction mechanism and a catalytic cycle based on a two-electron process is proposed. Finally, the synthetic utilities of the product are showcased by means of the transformations of the terminal olefin group and the ketone group.
- Shi, Chang-Yun,Yin, Liang,Zhang, Qi,Zhou, Si-Wei
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supporting information
p. 26351 - 26356
(2021/11/09)
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- Effective and Selective Catalysts for Cinnamaldehyde Hydrogenation: Hydrophobic Hybrids of Metal–Organic Frameworks, Metal Nanoparticles, and Micro- and Mesoporous Polymers
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Metal–organic frameworks (MOFs) as selectivity regulators for catalytic reactions have attracted much attention, especially MOFs and metal nanoparticle (NP) shelled structures, e.g., MOFs@NPs@MOFs. Nevertheless, making hydrophilic MOF shells for gathering hydrophobic reactants is challenging. Described here is a new and viable approach employing conjugated micro- and mesoporous polymers with iron(III) porphyrin (FeP-CMPs) as a new shell to fabricate MIL-101@Pt@FeP-CMP. It is not only hydrophobic and porous for enriching reactants, but also possesses iron sites to activate C=O bonds, thereby regulating the selectivity for cinnamyl alcohol in the hydrogenation of cinnamaldehyde. Interestingly, MIL-101@Pt@FeP-CMPsponge can achieve a high turnover frequency (1516.1 h?1), with 97.3 % selectivity for cinnamyl alcohol at 97.6 % conversion.
- Yuan, Kuo,Song, Tianqun,Wang, Dawei,Zhang, Xiaotao,Gao, Xiong,Zou, Ye,Dong, Huanli,Tang, Zhiyong,Hu, Wenping
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supporting information
p. 5708 - 5713
(2018/03/27)
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- Rhodium-Catalyzed Synthesis of α,β-Unsaturated Ketones through Sequential C-C Coupling and Redox Isomerization
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A novel Rh(I)-catalyzed sequential C-C coupling and redox isomerization between allylic alcohols and 1,3-dienes has been accomplished. This versatile protocol provides expeditious access to a broad range of polysubstituted α,β-unsaturated ketones with excellent atom economy and regioselectivity.
- Li, Hong-Shuang,Guo, Guili,Zhang, Rui-Ze,Li, Fei
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supporting information
p. 5040 - 5043
(2018/08/24)
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- A substituted cinnamic alcohol compound of preparation method
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The invention belongs to the field of medical and chemical intermediates and related chemical techniques, and relates to a preparation method of a substituted cinnamyl alcohol compound. Cinnamyl aldehyde and derivatives thereof are taken as raw materials, and nano-porous gold is taken as a catalyst, hydrogen is taken as a hydrogen source, organic alkali is taken as a solvent, and the hydrogen is selectively added to prepare substituted cinnamyl alcohol. Reaction temperature is -50 to 150 DEG C, reaction time is 12 to 36 h, and the hydrogen pressure is 1 to 50 bar; the molar ratio of the cinnamyl aldehyde and derivatives thereof to the catalyst is 1:0.01 to 0.1. The preparation method provided by the invention has the beneficial effects that the product selectivity is high, the repeatability of the catalyst is good, and the catalytic effect of the catalyst cannot obviously reduce after being reused for multiple times; the cheap green hydrogen is taken as the hydrogen source so as to meet the atom economy, and the possibility of industrialization is provided.
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Paragraph 0043; 0044; 0045; 0046; 0047; 0048; 0049; 0050
(2017/08/25)
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- A plug intermediate body west that card 3 - (3-trifluoromethyl phenyl) propanol method for the synthesis of (by machine translation)
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The invention discloses a plug intermediate body west that card 3 - (3-trifluoromethyl phenyl) propanol synthetic method, including: the trifluoromethyl benzaldehyde dissolved in a solvent, adding wittig agents and organic alkali, in 0-100 °C under a temperature condition after the reaction is complete, the post-processed to obtain 3 - (3-trifluoromethyl phenyl) 2-propen -1 alcohol; to 3 - (3-trifluoromethyl phenyl) 2-propen -1 catalyst Pd/C alcohol solution added in, and pressurized hydrogenation, in 0-60 °C under a temperature condition after the reaction is complete, the post-processed to obtain 3 - (3-trifluoromethyl phenyl) propanol. The preparation process of the present invention the easily obtained raw material used, the cost is low, and the reaction is controllable, the test operation is simplified, the operation is simple, is easy to deal with, high yield of the product, and can be operated continuously, is suitable for industrial production. (by machine translation)
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Paragraph 0017
(2016/11/17)
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- PROCESSES FOR THE PREPARATION OF CINACALCET
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The present invention provides processes and intermediates for preparing cinacalcet base and pharmaceutically acceptable salts thereof.
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Page/Page column 9
(2012/12/14)
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- PROCESSES FOR THE PREPARATION OF CINACALCET
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The present invention provides processes and intermediates for preparing cinacalcet base and pharmaceutically acceptable salts thereof.
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Page/Page column 23-24
(2011/04/19)
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- AMINE COMPOUND AND PHARMACEUTICAL USE THEREOF
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Provided is a novel amine compound represented by the following formula (I) having a superior peripheral blood lymphocyte decreasing action and superior in the immunosuppressive action, rejection suppressive action and the like, which shows decreased side effects of, for example, bradycardia and the like, or a pharmaceutically acceptable acid addition salt thereof, or a hydrate thereof, or a solvate thereof. wherein each symbol is as defined in the specification.
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Page/Page column 175
(2010/04/25)
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- Regio- and stereoselective heck α-arylation of cinnamyl alcohols
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The Heck reaction of cinnamyl alcohols with aryl iodides has been investigated using n-Bu4NOAc as the base in toluene. Under these conditions, the reaction affords regio- and stereoselectively (Z)-2,3-diarylallylic alcohols in moderate to good yields. Experimental evidence suggests that the observed selectivity in formation of the vinylic substitution products is kinetic in origin under these conditions and that both the base and the solvent play a key role. Georg Thieme Verlag Stuttgart.
- Ambrogio, Ilaria,Cacchi, Sandro,Fabrizi, Giancarlo,Goggiamani, Antonella,Sgalla, Simona
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experimental part
p. 620 - 624
(2009/07/11)
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- Synthesis of oxadiazole-2-oxide analogues as potential antischistosomal agents
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The synthesis of several 1,2,5-oxadiazole-2-oxide (Furoxan) analogues is described herein. These compounds were prepared in an effort to probe the SAR around the phenyl substituent and oxadiazole core for our studies toward thioredoxin-glutathione reductase (TGR) inhibition and antischistosomal activity.
- Rai, Ganesha,Thomas, Craig J.,Leister, William,Maloney, David J.
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supporting information; experimental part
p. 1710 - 1713
(2009/07/05)
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- Structure mechanism insights and the role of nitric oxide donation guide the development of oxadiazole-2-oxides as therapeutic agents against schistosomiasis
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Schistosomiasis is a chronic parasitic disease affecting hundreds of millions of individuals worldwide. Current treatment depends on a single agent, praziquantel, raising concerns of emergence of resistant parasites. Here, we continue our explorations of an oxadiazole-2-oxide class of compounds we recently identified as inhibitors of thioredoxin glutathione reductase (TGR), a selenocysteine-containing flavoenzyme required by the parasite to maintain proper cellular redox balance. Through systematic evaluation of the core molecular structure of this chemotype, we define the essential pharmacophore, establish a link between the nitric oxide donation and TGR inhibition, determine the selectivity for this chemotype versus related reductase enzymes, and present evidence that these agents can be modified to possess appropriate drug metabolism and pharmacokinetic properties. The mechanistic link between exogenous NO donation and parasite injury is expanded and better defined. The results of these studies verify the utility of oxadiazole-2-oxides as novel inhibitors of TGR and as efficacious antischistosomal agents. 2009 American Chemical Society.
- Rai, Ganesha,Sayed, Ahmed A.,Lea, Wendy A.,Luecke, Hans F.,Chakrapani, Harinath,Prast-Nielsen, Stefanie,Jadhav, Ajit,Leister, William,Shen, Min,Inglese, James,Austin, Christopher P.,Keefer, Larry,Arnér, Elias S. J.,Simeonov, Anton,Maloney, David J.,Williams, David L.,Thomas, Craig J.
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supporting information; experimental part
p. 6474 - 6483
(2010/03/31)
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- Mechanistic analysis of the photocycloaddition of silyl-tethered alkenes
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(Chemical Equation Presented) The photochemistry of substituted cinnamyloxy silanes has been examined in both cyclohexane and acetonitrile solvents. Alkene isomerization occurs in addition to cycloaddition. Fluorescence quantum yields and excited singlet state lifetimes have been determined for each compound. We have used the information in order to better understand the regio- and stereoselectivity of photocycloaddition between silyl-tethered cinnamyl groups. This study allows us to conclude that the 2 + 2 photocycloaddition between alkenes is not a Woodward-Hoffmann orbital symmetry controlled event. The most consistent explanation for the excellent regio- and stereoselectivity is that the photocycloaddition is conformationally controlled.
- Fleming, Steven A.,Parent, Alexander A.,Parent, Ephraim E.,Pincock, James A.,Renault, Lise
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p. 9464 - 9470
(2008/03/14)
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