- Preparation method of ilepcimide
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The invention provides a preparation method of ilepcimide. The preparation method comprises the following step: in the presence of a catalyst, reacting raw materials containing 4-bromo-1, 2-methylenedioxybenzene, an acrylate compound and piperidine to obtain the ilepcimide. The preparation method disclosed by the invention is good in selectivity, reduces side reactions, increases the conversion rate and yield of the product, reduces the use of toxic and irritant raw materials, saves the treatment cost of three wastes, is a green and environment-friendly process, and is suitable for industrial production, and the molar yield is 76% or above, and the purity is 99% or above.
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Paragraph 0050-0051; 0054-0055; 0058-0059
(2021/10/11)
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- Ternary Catalysis Enabled Three-Component Asymmetric Allylic Alkylation as a Concise Track to Chiral α,α-Disubstituted Ketones
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Multicomponent reactions that involve interception of onium ylides through Aldol, Mannich, and Michael addition with corresponding bench-stable acceptors have demonstrated broad applications in synthetic chemistry. However, because of the high reactivity and transient survival of these in situ generated intermediates, the substitution-type interception process, especially the asymmetric catalytic version, remains hitherto unknown. Herein, a three-component asymmetric allylation of α-diazo carbonyl compounds with alcohols and allyl carbonates is disclosed by employing a ternary cooperative catalysis of achiral Pd-complex, Rh2(OAc)4, and chiral phosphoric acid CPA. This method represents the first example of three-component asymmetric allylic alkylation through an SN1-type trapping process, which involves a convergent assembly of two active intermediates, Pd-allyl species, and enol derived from onium ylides, providing an expeditious access to chiral α,α-disubstituted ketones in good to high yields with high to excellent enantioselectivity. Combined experimental and computational studies have shed light on the mechanism of this novel three-component reaction, including the critical role of Xantphos ligand and the origin of enantioselectivity.
- Chang, Wenju,Fu, Xiang,Hu, Wenhao,Kang, Zhenghui,Liang, Yong,Tian, Xue,Xu, Xinfang,Zhao, Wenxuan
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p. 20818 - 20827
(2021/12/17)
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- Synthesis of Allylsilanes via Nickel-Catalyzed Cross-Coupling of Silicon Nucleophiles with Allyl Alcohols
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NiCl2(PMe3)2-catalyzed reaction of allyl alcohols with silylzinc reagents, including PhMe2SiZnCl, Ph2MeSiZnCl, and Ph3SiZnCl, was performed, achieving allylsilanes in high yields. Aryl- and heteroaryl-substituted allyl alcohols, (E)-3-arylprop-2-en-1-ols, 1-aryl-prop-2-en-1-ols, and (E)-1-phenylpent-1-en-3-ol can be employed in the transformation. A range of functional groups as well as heteroaryl groups were tolerated. Reaction exhibited high regioselectivity and E/Z-selectivity when 1- or 3-aryl-substituted allyl alcohols were used as the substrates. Reaction of chiral allyl alcohol, (S,E)-1-phenylpent-1-en-3-ol, yielded a configuration-inversion product (R,E)-dimethyl(phenyl)(1-phenylpent-1-en-3-yl)silane.
- Yang, Bo,Wang, Zhong-Xia
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supporting information
p. 7965 - 7969
(2019/10/19)
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- Total syntheses of surinone B, alatanones A–B, and trineurone A
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The total syntheses of four polyketides, surinone B (1), alatanones A–B (2–3), and trineurone A (4) were accomplished through an efficient and unified strategy via one-pot C-acylation reaction coupling 1,3-cyclohexadiones with EDC-activated acids under mild conditions. Alatanone A (2) was found to be a potent anti-microbial agent against Gram-positive and Gram-negative bacteria with MIC 31.25?μg/ml while alatanone B (3) was found to be a potent anti-fungal agent against Cladosporium cladosporioides with MIC 62.5?μg/ml compared to cycloheximide MIC 125?μg/ml. Our methodology allows performing kilogram scale of these scarce polyketides for the development of new antimicrobials.
- Gundoju, Narayana Rao,Bokam, Ramesh,Yalavarthi, Nageswara Rao,Buddana, Sudheer Kumar,Prakasham,Ponnapalli, Mangala Gowri
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- Ligand-accelerated non-directed C-H functionalization of arenes
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The directed activation of carbon-hydrogen bonds (C-H) is important in the development of synthetically useful reactions, owing to the proximity-induced reactivity and selectivity that is enabled by coordinating functional groups. Palladium-catalysed non-directed C-H activation could potentially enable further useful reactions, because it can reach more distant sites and be applied to substrates that do not contain appropriate directing groups; however, its development has faced substantial challenges associated with the lack of sufficiently active palladium catalysts. Currently used palladium catalysts are reactive only with electron-rich arenes, unless an excess of arene is used, which limits synthetic applications. Here we report a 2-pyridone ligand that binds to palladium and accelerates non-directed C-H functionalization with arene as the limiting reagent. This protocol is compatible with a broad range of aromatic substrates and we demonstrate direct functionalization of advanced synthetic intermediates, drug molecules and natural products that cannot be used in excessive quantities. We also developed C-H olefination and carboxylation protocols, demonstrating the applicability of our methodology to other transformations. The site selectivity in these transformations is governed by a combination of steric and electronic effects, with the pyridone ligand enhancing the influence of sterics on the selectivity, thus providing complementary selectivity to directed C-H functionalization.
- Wang, Peng,Verma, Pritha,Xia, Guoqin,Shi, Jun,Qiao, Jennifer X.,Tao, Shiwei,Cheng, Peter T. W.,Poss, Michael A.,Farmer, Marcus E.,Yeung, Kap-Sun,Yu, Jin-Quan
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p. 489 - 493
(2017/11/28)
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- Stereoselective and Site-Specific Allylic Alkylation of Amino Acids and Small Peptides via a Pd/Cu Dual Catalysis
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We report a stereoselective and site-specific allylic alkylation of Schiff base activated amino acids and small peptides via a Pd/Cu dual catalysis. A range of noncoded α,α-dialkyl α-amino acids were easily synthesized in high yields and with excellent enantioselectivities (up to >99% ee). Furthermore, a direct and highly stereoselective synthesis of small peptides with enantiopure α-alkyl or α,α-dialkyl α-amino acids residues incorporated at specific sites was accomplished using this dual catalyst system.
- Huo, Xiaohong,He, Rui,Fu, Jingke,Zhang, Jiacheng,Yang, Guoqiang,Zhang, Wanbin
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supporting information
p. 9819 - 9822
(2017/08/02)
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- Bioactivity and structure-activity relationship of cinnamic acid esters and their derivatives as potential antifungal agents for plant protection
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A series of cinnamic acid esters and their derivatives were synthesized and evaluated for antifungal activities in vitro against four plant pathogenic fungi by using the mycelium growth rate method. Structure-activity relationship was derived also. Almost all of the compounds showed some inhibition activity on each of the fungi at 0.5 mM. Eight compounds showed the higher average activity with average EC50 values of 17.4-28.6 μg/mL for the fungi than kresoxim-methyl, a commercial fungicide standard, and ten compounds were much more active than commercial fungicide standards carbendazim against P. grisea or kresoxim-methyl against both P. grisea and Valsa Mali. Compounds C1 and C2 showed the higher activity with average EC50 values of 17.4 and 18.5 μg/mL and great potential for development of new plant antifungal agents. The structure-activity relationship analysis showed that both the substitution pattern of the phenyl ring and the alkyl group in the alcohol moiety significantly influences the activity. There exists complexly comprehensive effect between the substituents on the phenyl ring and the alkyl group in the alcohol moiety on the activity. Thus, cinnamic acid esters showed great potential the development of new antifungal agents for plant protection due to high activity, natural compounds or natural compound framework, simple structure, easy preparation, low-cost and environmentally friendly.
- Zhou, Kun,Chen, Dongdong,Li, Bin,Zhang, Bingyu,Miao, Fang,Zhou, Le
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- A computational triage approach to the synthesis of novel difluorocyclopentenes and fluorinated cycloheptadienes using thermal rearrangements
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Electronic structure calculations have been used for the effective triage of substituent effects on difluorinated vinylcyclopropane precursors and their ability to undergo vinyl cyclopropane rearrangements (VCPR). Groups which effectively stabilised radicals, specifically heteroarenes, were found to result in the lowest energy barriers. Ten novel precursors were synthesised to test the accuracy of computational predictions; the most reactive species which contained heteroarenes underwent thermal rearrangements at room temperature to afford novel difluorocyclopentenes and fluorinated benzocycloheptadienes through competing VCPR and [3,3]-rearrangement pathways, respectively. More controlled rearrangement of ethyl 3-(1′(2′2′-difluoro-3′-benzo[d][1,3]dioxol-5-yl)cyclopropyl)propenoate (22) allowed these competing pathways to be monitored at the same time and activation energies for both reactions were determined; Ea(VCPR) = (23.4 ± 0.2) kcal mol-1 and Ea([3,3]) = (24.9 ± 0.3) kcal mol-1. Comparing our calculated activation energies with these parameters showed that no single method stood out as the most accurate for predicting barrier heights; (U)M05-2X/6-31+G? methodology remained the best for VCPR but M06-2X/6-31G? was better for the [3,3]-rearrangement. The consistency observed with (U)B3LYP/6-31G? calculations meant that it came closest to a universal method for dealing with these systems. The developed computational design model correctly predicted the observed selectivity of rearrangement pathways for both our system and literature compounds.
- Orr, David,Percy, Jonathan M.,Harrison, Zo? A.
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p. 6369 - 6380
(2016/10/03)
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- Chiral Cyclopentadienyl Iridium(III) Complexes Promote Enantioselective Cycloisomerizations Giving Fused Cyclopropanes
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The cyclopentadienyl (Cp) group is a very important ligand for many transition-metal complexes which have been applied in catalysis. The availability of chiral cyclopentadienyl ligands (Cpx) lags behind other ligand classes, thus hampering the investigation of enantioselective processes. We report a library of chiral CpxIrIII complexes equipped with an atropchiral Cp scaffold. A robust complexation procedure reliably provides CpxIrIII complexes with tunable counterions. In a proof-of-concept application, the iodide-bearing members are shown to be highly selective for enyne cycloisomerization reactions. The dehydropiperidine-fused cyclopropane products are formed in good yields and enantioselectivities.
- Dieckmann, Michael,Jang, Yun-Suk,Cramer, Nicolai
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supporting information
p. 12149 - 12152
(2015/10/12)
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- NOVEL PIPERINE DERIVATIVE AND USE THEREFOR
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The present invention provides novel piperine derivatives. The present pharmaceutical or food composition containing a piperine derivative as an active ingredient is very effective in preventing or treating metabolic diseases including obesity, diabetes,
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Paragraph 0055; 0056
(2015/01/16)
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- Tandem allylic oxidation-condensation/esterification catalyzed by silica gel: An expeditious approach towards antimalarial diaryldienones and enones from natural methoxylated phenylpropenes
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A new one-pot strategy has been developed, wherein abundantly available methoxylated phenylpropenes are directly transformed into corresponding dienones (1,5-diarylpenta-2,4-dien-1-ones) and enones (chalcones and cinnamic esters) via allylic oxidation-condensation or allylic oxidation-esterification sequences. Preliminary antimalarial activity studies of the above synthesized diaryldienones and enones against Plasmodium falciparum (Pf3D7) have shown them to be promising lead candidates for developing newer and economical antimalarial agents. In particular, two enones (12b and 13b) were found to possess comparatively better activity (IC50 = 4.0 and 3.4 μM, respectively) than licochalcone (IC50 = 4.1 μM), a well known natural antimalarial compound. The Royal Society of Chemistry 2011.
- Sharma, Abhishek,Sharma, Naina,Shard, Amit,Kumar, Rakesh,Mohanakrishnan, Dinesh,Saima,Sinha, Arun K.,Sahal, Dinkar
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p. 5211 - 5219
(2011/08/07)
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- Synthesis of some phenylpropanoid glycosides (PPGs) and their acetylcholinesterase/xanthine oxidase inhibitory activities
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In this research, three categories of phenylpropanoid glycosides (PPGs) were designed and synthesized with PPGs isolated from Rhodiola rosea L. as lead compounds. Their inhibitory abilities toward acetylcholinesterase (AChE) and xanthine oxidase (XOD) were also tested. Some of the synthetic PPGs exhibited excellent enzyme inhibitory abilities.
- Li, Xiao-Dong,Kang, Shuai-Tao,Li, Guo-Yu,Li, Xian,Wang, Jin-Hui
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experimental part
p. 3580 - 3596
(2011/07/07)
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- SULFONAMIDE CONTAINING COMPOUNDS AND USES THEREOF
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Compounds that modulate GHS-R are described herein.
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Page/Page column 55-56
(2010/10/03)
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- INDUCIBLE NITRIC OXIDE SYNTHASE DIMERIZATION INHIBITORS
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The present invention relates to compounds and methods useful as inhibitors of nitric oxide synthase. Certain compounds of the subject invention have the following structural formula: wherein T, X, and Y are independently selected from the group consisting of CR4, N, NR4, S, and O; U is selected from the group consisting of CR10 and N; V is selected from the group consisting of CR4 and N; W and W' are independently selected from the group consisting of CH2, CR7R8, NR9, O, N(O), S(O)q and C(O); n, m and p are independently an integer from 0 to 5; q is 0, 1, or 2; and other substituents are as defined herein. Other compounds of the subject invention have structural formulas as defined herein. Also disclosed herein are pharmaceutical compositions comprising the compounds of the subject invention
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Page/Page column 58
(2010/11/08)
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- Inhibition of uridine phosphorylase: Synthesis and structure-activity relationships of aryl-substituted 5-benzyluracils and 1-[(2- hydroxyethoxy)methyl]-5-benzyluracils
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A series of 1-[(2-hydroxyethoxy)methyl]-5-benzyluracils were synthesized and tested for inhibition of murine liver uridine phosphorylase (UrdPase). Inhibitors of UrdPase are reported to enhance the chemotherapeutic utility of 5-fluoro-2'-deoxyuridine and 5-fluorouracil and to ameliorate zidovudine- induced anemia in animal models. We prepared a series of 5-aryl-substituted analogues of 5-benzylacyclouridine (BAU), a good inhibitor of UrdPase (IC50 of 0.46 μM), to develop a compound with enhanced potency and improved pharmacokinetics. The first phase of structure-activity relationship studies on a series of 32 aryl-substituted 5-benzyluracils found several 5-(3- alkoxybenzyl) analogues of 5-benzyluracil with enhanced potency. The acyclovir side chain, the (2-hydroxyethoxy)methyl group, was substituted on the more potent aryl-substituted 5-benzyluracils. The two most potent compounds, 10y (3-propoxy) and 10dd (3-sec-butoxy), were inhibitors of UrdPase with IC50s of 0.047 and 0.027 μM, respectively. Six compounds were tested in vivo for effects on steady-state concentrations of circulating uridine in rats. Plasma uridine levels were elevated 3-9-fold by compound levels that ranged from 8 to 50 μM.
- Orr,Musso,Boswell,Kelley,Joyner,Davis,Baccanari
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p. 3850 - 3856
(2007/10/02)
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- A NOVEL ROUTE TO α,β-UNSATURATED ESTERS VIA A REFORMATSKY-TYPE REACTION USING SODIUM TELLURIDE
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Sodium telluride, prepared by heating tellurium and sodium hydride in a 1:2 molar ratio in dry N,N-dimethylformamide, readily debrominates a bromoacetic ester at low temperatures to generate an enolate anion, which undergoes a Reformatsky-type reaction with various non-enolizable aldehydes to give the corresponding α,β-unsaturated esters in good to moderate yields.Ketones remain almost unaffected under the same conditions.
- Suzuki, Hitomi,Inouye, Masahiko
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p. 403 - 406
(2007/10/02)
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