- Preparation of tetrasubstituted olefins using mono or double aerobic direct C-H functionalization strategies: Importance of steric effects
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A novel protocol for the synthesis of tetrasubstituted olefins through a biomimetic approach has been explored. Both mono- and diarylations were performed under ambient oxygen pressure, giving a range of highly hindered tetrasubstituted alkenes. For diarylation of disubstituted substrates, it was demonstrated that the second arylation is the rate-limiting step of the overall transformation.
- Gigant, Nicolas,Quintin, Franc?ois,B?ckvall, Jan-E.
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- Copper-catalyzed radical oxyallylation of olefins for the construction of alkene-containing isoxazolines
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A radical-mediated approach to alkene oxyallylation using allylic oximes is described. The reaction proceeds under copper-catalytic redox-neutral conditions and tolerates various functional groups. This protocol thus enables the synthesis of structurally valuable isoxazolines and the introduction of a versatile olefin motif in a single step.
- He, Xiaoxue,Qian, Lijie,Dai, Yuyu,Yan, Xinhuan,Li, Xiaoqing,Xu, Xiangsheng
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supporting information
(2021/05/31)
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- Reaction type ultraviolet light absorber and preparation method and application thereof
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The invention discloses a reaction type ultraviolet light absorber as well as a preparation method and application thereof. The method is characterized by comprising the following steps; with paraformaldehyde as an initial raw material, synthesizing 2-(bromomethyl) methyl acrylate; then carrying out a reaction on the 2-(bromomethyl) methyl acrylate and 2,2',4,4'-dichlorophenol as a reactant by controlling the temperature, and the types of the solvents and alkalis to obtain the reaction type ultraviolet light absorber. The reaction type ultraviolet light absorber contains unsaturated carbon-carbon double bonds, wherein the main ultraviolet light absorption range is 250-400 nm; the reaction type ultraviolet light absorber is a novel broad-spectrum ultraviolet light absorber, the synthesis process is convenient to operate, the raw materials are low in price and easy to obtain, and the reaction type ultraviolet light absorber has very high market value and application value.
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Paragraph 0047-0049
(2020/07/03)
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- COMPOSITIONS AND METHODS FOR PROTEIN LABELING, MODIFICATION, ANALYSIS, AND TARGETED DELIVERY
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The invention relates to chemically reactive and/or biologically active compounds, reagents and compositions thereof. More particularly, the invention provides novel reagents that are useful in chemical synthesis, functionalization, delivery, probing and/or analytical measurements of small molecule drugs, proteins, antibodies and other biomolecules. The invention provides novel biologically active agents useful as diagnostics or therapeutics, and related composition and methods of uses thereof.
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Paragraph 00218
(2020/01/24)
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- Photoredox-Coupled F-Nucleophilic Addition: Allylation of gem-Difluoroalkenes
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A novel strategy for the expedient construction of CF3-embeded tertiary/quarternary carbon centers was developed by taking advantage of photoredox catalysis. Thanks to a key step of single-electron oxidation, electron-rich gem-difluoroalkenes, which otherwise are essentially reluctant towards F-nucleoplilic addition, now readily participate in this fluoroallylation reaction. Furthermore, this strategy provides an elegant example for the generation, as well as functionalization, of α-CF3-substituted benzylic radical intermediates using cheap and readily available starting materials.
- Liu, Haidong,Ge, Liang,Wang, Ding-Xing,Chen, Nan,Feng, Chao
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supporting information
p. 3918 - 3922
(2019/02/19)
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- Photoredox Decarboxylative Alkylation/(2+2+1) Cycloaddition of 1,7-Enynes: A Cascade Approach Towards Polycyclic Heterocycles Using N-(Acyloxy)phthalimides as Radical Source
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No Abstract. (Figure presented.).
- Correia, José Tiago Menezes,Piva da Silva, Gustavo,André, Elias,Paix?o, Márcio Weber
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supporting information
p. 5558 - 5564
(2019/09/16)
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- Preparation method of 5,5-dimethyl-3-methylene pyrrolidine-2-ketone
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The invention discloses a preparation method of 5,5-dimethyl-3-methylene pyrrolidine-2-ketone. The preparation method comprises the following steps: (S1) under the action of strong organic alkali, formaldehyde and a compound I generate condensation reaction to obtain a compound II; (S2) the compound II and a halogenating reagent generate halogenating reaction to obtain a compound III; (S3) under the action of the strong organic alkali, the compound III and 2-nitropropane generate substitution reaction to obtain a nitryl-containing compound IV; (S4) the compound IV carries out domino reaction of reducing nitryl and closing rings under the action of a catalyst and a reducing agent to obtain the 5,5-dimethyl-3-methylene pyrrolidine-2-ketone. The preparation method disclosed by the invention has the beneficial effects that the synthetic steps are fewer, the implementation is simple and easy, no harsh reaction condition is needed, the process route is novel, the yield is more than 50%, andthe reaction heat and gas generation is well controlled. The preparation method disclosed by the invention has the characteristics of novel process route, relatively mild reaction conditions, easy expansion, large-scale production and the like.
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Paragraph 0018
(2018/04/28)
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- Factors influencing the cytotoxicity of α-methylene-γ-hydroxy esters against pancreatic cancer
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A systematic study to identify the factors influencing the cytotoxicity of α-methylene-γ-hydroxy esters against three pancreatic cancer cell lines (Panc-1, MIA-PaCa-2, and BxPC-3) has established that, in addition to Michael acceptor abilities, the possibility to lactonize to α-methylene-γ-butyrolactones is as important. The substitution pattern and the number of carbons between the hydroxy and ester moieties also influence the bio-activity.
- Ramachandran, P. Veeraraghavan,Helppi, Matthew A.,Lehmkuhler, Arlie L.,Marchi, Jennifer M.,Schmidt, C. Max,Yip-Schneider, Michele T.
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supporting information
p. 4270 - 4273
(2015/11/03)
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- Synthesis of the major metabolites of febuxostat
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Total synthesis of three Febuxostat metabolites, named 67M-1, 67M-2, and 67M-4,is described in this article. Through condensation of the key intermediate compound A with different side chains, and then oxidation and hydrolysis, we obtained three target compounds with an overall yield of 19.5%-28.0%.
- Li, Xiao Long,Qiu, Rui,Wan, Wei Li,Cheng, Xu,Hai, Li,Wu, Yong
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p. 217 - 221
(2015/06/23)
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- Synthesis, in vitro, and in vivo evaluation of novel functionalized quaternary ammonium curcuminoids as potential anti-cancer agents
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Novel functionalized quaternary ammonium curcuminoids have been synthesized from piperazinyl curcuminoids and Baylis-Hillman reaction derived allyl bromides. These molecules are found to be highly water soluble with increased cytotoxicity compared to native curcumin against three cancer cell lines MIAPaCa-2, MDA-MB-231, and 4T1. Preliminary in vivo toxicity evaluation of a representative curcuminoid 5a in healthy mice indicates that this molecule is well tolerated based on normal body weight gains compared to control group. Furthermore, the efficacy of 5a has been tested in a pancreatic cancer xenograft model of MIAPaCa-2 and has been found to exhibit good tumor growth inhibition as a single agent and also in combination with clinical pancreatic cancer drug gemcitabine.
- Solano, Lucas N.,Nelson, Grady L.,Ronayne, Conor T.,Lueth, Erica A.,Foxley, Melissa A.,Jonnalagadda, Sravan K.,Gurrapu, Shirisha,Mereddy, Venkatram R.
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p. 5777 - 5780
(2015/11/24)
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- 4-(Dimethylamino)pyridine as a catalyst for the lactonization of 4-hydroxy-2-methylenebutanoate esters
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The catalytic action of 4-(dimethylamino)pyridine (DMAP) in lactonizing 4-hydroxy-2-methylenebutanoate esters to 2-methylene-γ-butyrolactones is described. The use of DMAP, which functions as an excellent complement to the more traditional acid-catalyzed lactonization protocol, allows for the synthesis of 2-methylene-γ-butyrolactones containing acid-sensitive groups under essentially neutral conditions.
- Nicponski, Daniel R.
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supporting information
p. 2075 - 2077
(2014/04/03)
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- Diastereoselective synthesis of α-(aminomethyl)-γ-butyrolactones via a catalyst-free aminolactonization
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An auto-catalytic domino reaction, presumably involving an aza-Michael reaction, proton transfer, and lactonization, furnishing α-(aminomethyl)-γ-butyrolactones in near quantitative yields and excellent diastereoselectivity is described.
- Ramachandran, P. Veeraraghavan,Nicponski, Daniel R.
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supporting information
p. 15216 - 15219
(2015/01/08)
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- Synthesis of enantiopure β2-homoalanine derivatives via rhodium catalyzed asymmetric hydrogenation
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The stereoselective synthesis of chiral β2-homoalanine derivatives with 99% ee by the Rh-catalyzed enantioselective hydrogenation of prochiral 2-aminomethyl acrylates is described. The subsequent transformation to chiral 3-amino-2-methylpropanols is also demonstrated.
- Luehr, Susan,Holz, Jens,Zayas, Odalys,Seidelmann, Oliver,Domke, Lutz,Boerner, Armin
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p. 395 - 401
(2013/06/27)
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- Synthesis and biological evaluation of novel benzoxaboroles as potential antimicrobial and anticancer agents
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Several novel benzoxaborole derivatives were synthesized starting from 2-formylphenylboronic acid utilizing Baylis-Hillman reaction, Barbier allylation, Passerini reaction, and aldol reaction protocols as the key step. All the synthesized benzoxaboroles have been evaluated for their antibacterial, antifungal, and anticancer activities.
- Sravan Kumar,Alam,Gurrapu, Shirisha,Nelson, Grady,Williams, Michael,Corsello, Michael A.,Johnson, Joseph L.,Jonnalagadda, Subash C.,Mereddy, Venkatram R.
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p. 814 - 820
(2013/08/23)
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- Synthesis and herbicidal activity of diphenyl ether derivatives containing unsaturated carboxylates
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A series of novel diphenyl ether derivatives containing unsaturated carboxylates were designed and synthesized. Their structures were identified by 1H nuclear magnetic resonance and elemental analyses. The bioassays indicated that the compounds 5b and 5c exhibited good herbicidal activities against velvetleaf at a concentration of 30-40 g/hm2. The relationship between structure and herbicidal activity was also discussed. Among unsaturated carboxylates group, butenoate is the most promising one. Amonst them, 4-ethoxy-4-oxobutenyl 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2- nitrobenzoate 5b was identified as the most promising candidate due to its high protoporphyrinogen IX oxidase inhibition effect (pI50 = 6.64) and good herbicidal activity against broadleaf weeds with selectivity to soybean and low toxicity to mammals.
- Yu, Haibo,Yang, Huibin,Cui, Dongliang,Lv, Liang,Li, Bin
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scheme or table
p. 11718 - 11726
(2012/04/04)
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- Regioselective radical bromoallylation of allenes leading to 2-bromo-substituted 1,5-dienes
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The regioselective radical bromoallylation of allenes proceeded efficiently in the presence of AIBN as a radical initiator to give 2-bromo-substituted 1,5-dienes in excellent yields. The addition of a bromine radical took place regioselectively onto the central carbon of allenes generating a stable allyl radical, which underwent addition/β-fragmentation reactions with allylbromides. The products could be further functionalized by Pd-catalyzed coupling reactions.
- Kippo, Takashi,Fukuyama, Takahide,Ryu, Ilhyong
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supporting information; experimental part
p. 3864 - 3867
(2011/09/15)
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- Structure-activity relationships of tulipalines, tuliposides, and related compounds as inhibitors of MurA
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The enzyme MurA performs an essential step in peptidoglycan biosynthesis and is therefore a target for the discovery of novel antibacterial compounds. We report here the inhibition of MurA by natural products from tulips (tulipalines and tuliposides), and the structure-activity relationships of various derivatives. The inhibition of MurA can be related to antibacterial activity, and MurA is probably one of the relevant molecular targets of the tulipaline derivatives. MurA inhibition by this class of compounds depends on the presence of the substrate UNAG, which indicates non-covalent suicide inhibition as observed previously for cnicin. With respect to selectivity, however, the reactivity against arbitrary sulfhydryl groups, such as in glutathione, could not yet be sufficiently separated from MurA inhibition in the present dataset.
- Mendgen, Thomas,Scholz, Therese,Klein, Christian D.
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supporting information; experimental part
p. 5757 - 5762
(2010/12/24)
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- Development of practical methodologies for the synthesis of functionalized benzoboroxoles
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2-Formylphenylboronic acids upon reaction with activated olefins such as acrylates, methyl vinyl ketone, and acrylonitrile provide functionalized benzoboroxoles. The corresponding homologated benzoboroxoles were synthesized via the reaction of 2-formylphenylboronic acids with α- bromomethylacrylates.
- Kumar, J. Sravan,Bashian, Christopher M.,Corsello, Michael A.,Jonnalagadda, Subash C.,Mereddy, Venkatram R.
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scheme or table
p. 4482 - 4485
(2010/10/01)
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- Synthesis of 2,3,4,7-tetrahydro-1H-azepines as privileged ligand scaffolds for the design of aspartic protease inhibitors via a ring-closing metathesis approach
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We have developed a short and highly efficient synthetic strategy towards the hitherto hardly known 3,5- and 3,6-disubstituted 2,3,4,7-tetrahydro-1H-azepine scaffold via a ring-closing metathesis approach utilizing inexpensive and readily available starti
- Brass, Sascha,Chan, Nan-Si,Gerlach, Christof,Luksch, Torsten,B?ttcher, Jark,Diederich, Wibke E.
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p. 5406 - 5422
(2007/10/03)
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- Isotactic N-alkyl acrylamide oligomers assume self-assembled sheet structure: First unequivocal evidence from crystal structures
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Herein we present the first unequivocal evidence of the ability of isotactic N-alkyl acrylamide oligomers to assume self-assembled sheet-like structures that are reminiscent of protein β-sheets. The Royal Society of Chemistry 2006.
- Kendhale, Amol,Gonnade, Rajesh,Rajamohanan, Pattuparampil R.,Sanjayan, Gangadhar J.
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p. 2756 - 2758
(2008/09/19)
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- P-hydroxyphenyl propionic acid derivatives as antiproliferative agents
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Derivatives of the compound p-hydroxyphenyl propionic acid characterised by those derivatives having the general formulas (I) and (Ia), where n can take the values 1,2,3; R can be H or CH3 and R1 can be CH3 or H with pharmacological activity and their application in medicine for the treatment of disorders of the immunological system.
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- Bromination of organic allylic compounds by using N,N′-dibromo-N,N′-1,2-ethane diyl bis(2,5-dimethyl benzene sulphonyl)amine
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N,N′-Dibromo-N,N′-1,2-ethane diyl bis(2,5-dimethyl benzene sulphonyl)amine is an efficient brominating agent for bromination of allylic positions of different organic compounds. This reagent in presence of benzoyl peroxide can brominates the allylic positions of organic compounds in ambient conditions in carbon tetrachloride.
- Khazaei, Ardeshir,Vaghei, Ramin Ghorbani,Karkhanei, Ebrahim
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p. 2107 - 2113
(2007/10/03)
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- Scavenger assisted combinatorial process for preparing libraries of tertiary amine compounds
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This invention relates to a novel solution phase process for the preparation of tertiary amine combinatorial libraries. These libraries have utility for drug discovery and are used to form wellplate components of novel assay kits.
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- Synthesis and biological activity of 4-amino-7-oxo-substituted analogoues of 5-Deaza-5,6,7,8-tetrahydrofolic acid and 5,10-dideaza-5,6,7,8- tetrahydrofolic acid
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The 4-amino-7-oxo-substituted analogues of 5-deaza-5,6,7,8- tetrahydrofolic acid (5-DATHF) and 5,10-dideaza-5,6,7,8-tetrahydrofolic acid (DDATHF) were synthesized as potential antifolates. Treatment of the α,β- unsaturated esters 11a-c, obtained in one synthetic step from commercially available para-substituted benzoates (9a-c) and methyl 2-(bromomethly)- acrylate (10), with malononitrile in NaOMe/MeOH afforded the corresponding pyridones 12a-c. Formation of the pyrido[2,3-d]pyrimidines 13a-c was accomplished upon treatment of 12a-c with guanidine in methanol. After the hydrolysis of the ester group present in 13a-c, the resulting carboxylic acids 14a-c were treated with diethyl cyanophosphonate in Et3N/DMF and coupled with L-glutamic acid dimethyl ester to give 15a-c. Finally, the basic hydrolysis of 15a-c yielded the desired 4-amino-7-oxo-substituted analogues 16a-c in 20-27% overall yield. Compounds 16a-c were tested in vitro against CCRF-CEM leukemia cells. The results obtained indicated that our 4-amino-7- oxo analogues are completely devoid of any activity, the IC50 being higher than 20 μg/mL for all cases except 14c for which a value of 6.7 μg/mL was obtained. These results seem to indicate that 16a-c are inactive precisely due to the presence of the carbonyl group in position C7, the distinctive feature of our synthetic methodology.
- Borrell,Teixido,Martinez-Teipel,Metallana,Copete,Llimargas,Gracia
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p. 3539 - 3545
(2007/10/03)
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- A FACILE, EFFICIENT ROUTE TO METHYL α-HYDROXYMETHYLACRYLATE AND METHYL α-HALOMETHYLACRYLATES
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DABCO-catalyzed coupling of formaldehyde and methyl acrylate provides the title hydroxy compound.Treatment with HBr conveniently affords the key synthetic intermediate methyl α-bromomethylacrylate in good overall yield.
- Drewes, Siegfried E.,Loizou, Georgia,Roos, Gregory H. P.
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p. 291 - 298
(2007/10/02)
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- AN EFFICIENT PREPARATION OF ALKYL α-BROMOMETHYLACRYLATES BY DEHYDROBROMINATION OF ALKYL β,β'-DIBROMOISOBUTYRATES WITH POTASSIUM FLUORIDE
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1 and 2 alkyl esters of β,β'-dibromoisobutyric acid are efficiently dehydrobrominated to alkyl α-bromomethylacrylates by anhydrous potassium fluoride (2.5 equiv) in refluxing acetonitrile/DMF (85:15). 3 isobutyrates give reduced yields of acrylates due to accompanying cleavage of the ester by the HF produced.
- Anzeveno, Peter B.,Campbell, Jeffrey A.,White, William L.
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p. 387 - 392
(2007/10/02)
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