- Tethered aminohydroxylation: Synthesis of the β-amino acid of microsclerodermins A and B
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The utility of the tethered aminohydroxylation (TA) has been demonstrated by synthesis of the complex β-amino acid residue of microsclerodermins A and B. The TA provided a regio- and stereoselective functionalization of a complex homoallylic alcohol. The route includes late-stage introduction of the aliphatic side chain via a cuprate addition and cross metathesis, a tactic designed to render the synthesis applicable to other microsclerodermins.
- Pullin, Robert D. C.,Rathi, Akshat H.,Melikhova, Ekaterina Y.,Winter, Christian,Thompson, Amber L.,Donohoe, Timothy J.
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- Electrochemical Conjugate Additions of the Allyl Groups in Substituted Allyl Halides to α,β-Unsaturated Esters
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Electrolysis of allyl halides and diethyl fumarate (2) in N,N-dimethylformamide containing 0.2 M tetraethylammonium tosylate gave a conjugate addition product, ethyl 3-(ethoxycarbonyl)-5-hexenoate, in a moderate yield.The electrochemical reaction of 1-chloro-3-methyl-2-butene (4) with 2, that of allyl chloride 4 with methyl crotonate (6), and that of methyl 4-halo-2-butenoate with 2 likewise gave the corresponding conjugate addition products, ethyl 3-(ethoxycarbonyl)-6-methyl-5-heptenoate, methyl 3,4,4-trimethyl-5-hexenoate, and ethyl 3-(ethoxycarbonyl)-4-(methoxycarbonyl)-5-hexenoate, respectively.The addition reaction of 4 to 2 takes place at the α-carbon terminus of 4 exclusively, whereas the addition of 4 to 6 at the γ-carbon terminus of 4 .These regioselectivities of the additions and pathways of the reactions are discussed.
- Satoh, Shohei,Suginome, Hiroshi,Tokuda, Masao
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- The total synthesis of the oxopolyene macrolide RK-397
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It works both ways: The convergent total synthesis of the oxopolyene macrolide RK-397 utilizes remote asymmetric induction and a two-directional chain synthesis to prepare the polyol portion of the molecule, as well as a cross-metathesis reaction of a trienal with a terminal alkene to append the polyene to the polyol. (Chemical Equation Presented).
- Mitton-Fry, Mark J.,Cullen, Aaron J.,Sammakia, Tarek
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- Ruthenium-catalyzed enantioselective C-H functionalization: A practical access to optically active indoline derivatives
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Ru(II)-catalyzed enantioselective C-H activation/hydroarylation has been developed for the first time, allowing for highly enantioselective synthesis of indoline derivatives via catalytic C-H activation. Commercially available Ru(II) arene complexes and chiral α-methylamines were employed as highly enantioselective catalysts. Based on a sterically rigidified chiral transient directing group, multisubstituted indolines were produced in up to 92% yield with 96% ee. Further transformation of the resulting 4-formylindoline enables access to an optically active tricyclic compound that is of potential biological and pharmaceutical interest.
- Li, Zhong-Yuan,Lakmal, Hetti Handi Chaminda,Qian, Xiaolin,Zhu, Zhenyu,Donnadieu, Bruno,McClain, Sarah J.,Xu, Xue,Cui, Xin
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supporting information
p. 15730 - 15736
(2019/10/11)
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- Chlorobenzene-pyridine compounds and application thereof
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The invention relates to chlorobenzene-pyridine compounds and an application thereof. The compounds can be used for preparing a Smoothened protein inhibitor and a drug for resisting adenocarcinoma andesophagus cancer and have the structure in the general formula (I) shown in the description, wherein X is selected from the structure shown in the description, R1 is selected from H or the structureshown in the description, and R2 is selected from the structure shown in the description.
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Paragraph 0112; 0117; 0118; 0119
(2018/04/01)
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- QUINAZOLINE DERIVATIVE, PREPARATION METHOD THEREFOR, AND PHARMACEUTICAL COMPOSITION AND APPLICATION THEREOF
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Disclosed are a quinazoline derivative, a preparation method therefor, and a pharmaceutical composition and an application thereof. The present invention provides a compound represented by general formula I, a stereoisomer thereof and a pharmaceutical acceptable salt or a solvate thereof. The quinazoline derivative of the present invention has a unique chemical structure, is characterized by irreversibly inhibiting EGFR tyrosine kinase, has high biological activity, apparently improves the inhibiting effect on the EGFR tyrosine kinase, has quite strong tumor inhibiting effect on tumor cells and a transplantation tumor pathological model of animal tumors, and has good market developing prospects.
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Paragraph 0134; 0135
(2017/07/14)
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- Oxoindole spiro-compound based on allyl sulfide ylide serving as C3 synthon and synthesis method thereof
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The invention relates to an oxoindole spiro-compound based on allyl sulfide ylide serving as a C3 synthon. The general chemical molecular formula is CHO, wherein m, n and x are respectively an integer of 1-10; the molecule has a structure as shown below in the specification; R is methyl, ethyl, acetyl, methylethyl ether, benzyl or di-tert-butyl dicarbonate; R is hydroxyl, methoxyl or ethoxyl; and R is 5-F, 5-Br, 5-Cl, 5-CH3, 5-OCH3, 6-Cl, 6-Br, 6-OCH3, 7-CH3, 7-Cl or 7-Br. The invention has the following advantages: through the characteristics of a tandem reaction, the method achieves the purpose of synthesizing the target product through one step, obviously improves the reaction efficiency, saves the reaction time and simplifies the reaction step, thereby providing a brand new method and idea for a trisubstituted five-element oxide spiro-compound, and providing a certain reference value for synthesis of similar compounds.
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Paragraph 0037-0039
(2017/12/06)
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- Pyrazolopyrimidine derivative, preparation method, pharmaceutical composition and application
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The invention discloses a pyrazolopyrimidine derivative, a preparation method, a pharmaceutical composition and application. The invention provides the pyrazolopyrimidine derivative as shown in a formula I and stereoisomer or solvate or pharmaceutically acceptable salts or active metabolite or prodrug thereof. The pyrazolopyrimidine derivative as shown in the formula I has good inhibitory activity on Bruton's tyrosine kinase (Btk) and particularly has good in vitro and in vivo inhibitory activity on growth of tumor cells, and a good marketization prospect is achieved. Please see the formula I in the description.
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Paragraph 0249; 0250; 0251
(2017/07/19)
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- Geminal silicon/zinc reagent as an equivalent of difluoromethylene bis-carbanion
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A new difluorinated reagent, [difluoro(trimethylsilyl)methyl]zinc bromide, bearing C-Zn and C-Si bonds is described. The reagent is conveniently prepared by cobalt-catalyzed halogen/zinc exchange. It can be coupled with two different C-electrophiles in a stepwise manner (with allylic halides for C-Zn bond and aldehydes for C-Si bond) affording products containing a difluoromethylene fragment.
- Kosobokov, Mikhail D.,Levin, Vitalij V.,Zemtsov, Artem A.,Struchkova, Marina I.,Korlyukov, Alexander A.,Arkhipov, Dmitry E.,Dilman, Alexander D.
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supporting information
p. 1438 - 1441
(2014/04/03)
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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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- A chemoenzymatic asymmetric synthesis of methyl (6S,13R)-6,13-dihydroxytetradeca-(2E,4E,8E)-trienoate, a component of Mycosphaerella rubella
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The first asymmetric synthesis of (6S,13R)-6,13-dihydroxytetradeca-(2E,4E,8E)-trienoate has been developed. The key steps of the synthesis were the use of an efficient lipase-catalyzed acylation, a chiral template-driven enantiocontrolled allylation for introducing the stereogenic centers, and a cross-metathesis for controlling the C-8 olefin geometry.
- Sharma, Anubha,Gamre, Sunita,Chattopadhyay, Subrata
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body text
p. 1164 - 1167
(2009/09/30)
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- FUSED PYRIMIDINONE MATRIX METALLOPROTEINASE INHIBITORS
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Selective MMP-13 inhibitors are fused pyrimidinones of the formula or a pharmaceutically acceptable salt thereof, wherein: W, together with the carbon atoms to which it is attached, form a 5-membered ring diradical X is O, S, SO, SO2, NR5, or CH 2; B is O or NR5; or A and B are taken together to form--C≡C--; R1, R4, and R 5 are hydrogen, alkyl, alkenyl, alkynyl, (CH2)n aryl, (CH2)n cycloalkyl, C1-C6 alkanoyl, or (CH2)n heteroaryl; R2 and R3 are hydrogen, alkyl, alkenyl, alkynyl CN, NO2, NR 4R5, (CH2)n cycloalkyl, (CH2) n aryl, or (CH2)n heteroaryl; R2 may further be halo; n is an integer of from 0 to 5; and R4 and R5 when taken together with a nitrogen to which they are both attached complete a 3-to 8-membered ring containing carbon atoms and optionally containing O, S, or N, and substituted or unsubstituted; with the proviso that R1 and R3 are not both selected from hydrogen and C1-C6 alkyl.
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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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- Synthetic and spectroscopic studies of structural analogs of piper amides - The 5-aryl-2E,4E-pentadienamides
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The methyl esters and piperidides of fourteen 5-aryl-2E,4E-pentadienoic acids have been synthesized starting from the corresponding aryl aldehydes.
- Banerji, Avijit,Banerjee, Tapasri,Sengupta, Ratna,Sengupta, Piyali,Das, Chittaranjan,Sahu, Anita
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p. 876 - 883
(2007/10/03)
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- EXO- and endohormones. XXII1: Synthesis of methyl (2E,4Z)-2,4-decadienoate, the pheromone synergist of the bark beetle Pityogenes chalcographus
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The synthesis of methyl (2E,4Z)-2,4-decadienoate was based on a C 4 + C6 scheme. The coupling reaction took place between the 1-hexanale and phosphonium salt of methyl 1-bromocrotonate in a Wittig condensation. Methyl (2E,4Z)-2,4-decadienoate is a minor component of the sex pheromone of the bark beetle Pityogenes chalcographus.
- Maxim, Sanda,Ganscǎ, Lucia,Oprean, Ioan,Budae, Iuliana
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p. 543 - 544
(2007/10/03)
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- Synthesis of homoallylic (but-3-enylic) alcohols from aldehydes with allylic chlorides, tin(II) chloride and potassium iodide in water
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Homoallylic (but-3-enylic) alcohols have been prepared in good yields by reductive allylation of aldehydes in water with various allylic chlorides in the presence of tin(II) chloride and potassium iodide. The Barbier type reaction with prop-2-ynyl chloride is also achieved under the same conditions.
- Houllemare, Didier,Outurquin, Francis,Paulmier, Claude
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p. 1629 - 1632
(2007/10/03)
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- SYNTHESIS OF AN ORALLY ACTIVE PAF ANTAGONIST OF THE N-PENTADIENAMIDE CLASS
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The PAF antagonist -5-(4-methoxyphenyl)-N--2,4-decadienamide (2) was synthesized from (S)-α-methyl-3-pyridinebutanol (14), which was obtained either from ethyl lactate or by enantioselective kinetic hydrolysis of its racemate using the lipase derived from Pseudomonas cepacia (syn.P. fluorescens).Mesylation of 14, followed by azide displacement and hydrogenation, produced amine (7), which was coupled with the p-nitrophenol ester (8) to give 2.The direct coupling of (E,E)-5-(4-methoxyphenyl)-2,4-decadienoic acid (27) with azide(24) in the presence of tri-n-butylphosphine also gave 2.Acid (27) was prepared by a vinylogous Reformatsky reaction between ketone (25) and methyl 4-bromocrotonate.
- Manchand, Percy S.,Schwartz, Alan,Wolff, Steven,Belica, Peter S.,Madan, Pradeep,et al.
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p. 1351 - 1369
(2007/10/02)
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- Synthesis of α-halo β,γ-unsaturated esters from γ-phenylseleno α,β-unsaturated esters
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γ-Phenylseleno α,β-unsaturated esters, prepared from α-phenylseleno aldehydes by Horner-Emmons reaction and treated with bromine or sulfuryl chloride, form adducts whose decomposition leads to α-halo β,γ-unsaturated esters in fair to good yields.
- Duclos, Jean-Francois,Outurquin, Francis,Paulmier, Claude
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p. 7417 - 7420
(2007/10/02)
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- Regioselective SN' allylic substitution versus 1,4-addition: Synthesis of α-substituted β,γ-unsaturated esters
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The reaction of the higher order organocuprate reagents R2Cu(CN)Li2-BF3 with γ-bromo α,β-unsaturated esters gives with very high selectivity α-substituted β,γ-unsaturated esters arising from a SN' allylic substitution. This reaction allows an easy access to α-silyl β,γ-unsaturated esters.
- Girard,Romain,Ahmar,Bloch
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p. 7399 - 7402
(2007/10/02)
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- Imidazolidinones as brain activators
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This invention relates to imidazolidinone compounds of the formula STR1 wherein Q is methylene group or a single bond: R is a heterocyclic group selected from the group consisting of pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl and 1,3-thiazolyl which may be unsubstituted or with a substituent selected from the group consisting of lower alkyl, lower alkoxy and halogen atom, wherein R is bonded to Q or, when Q is a single bond, to the imidazolidinone ring, through the carbon atom of R; the ring A is an unsubstituted phenyl or a substituted phenyl having 1 or 2 substituent(s) selected from the group consisting of lower alkyl, lower alkoxy, halogen, lower alkylthio, trihalogeno-lower alkyl and nitro; Y is vinylene group or ethynylene; m is a integer from 1 to 6 and n is 0, 1 or 2, or a pharmacetically acceptable salt thereof. These compounds aer useful as cerebral activators, anti-depressants and nootropic drugs.
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- SYNTHESIS AND CHARACTERIZATION OF ALL FOUR ISOMERS OF METHYL 2,4-DECADIENOATE FOR AN INVESTIGATION OF THE PHEROMONE COMPONENTS OF Pityogenes chalcographus
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Methyl (2E,4Z)-2,4-decadienoate (1), an important pheromone component of Pityogenes calcographus, and its three geometrical isomers (2-4) have been synthesized and obtained in >99percent isomeric purity.Urea inclusion complexes were used in the final purification procedures.Spectroscopic data (MS, (1)H and (13)C NMR) of all four isomers are discussed.A photoisomerization study of the decadienoates is presented.
- Baeckstroem, Peter,Jacobsson, Ulla,Norin, Torbjoern,Unelius, C. Rikard
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p. 2541 - 2548
(2007/10/02)
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- Allylic Selenides in Organic Synthesis: New Methods for the Synthesis of Allylic Amines
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Oxidative rearrangement of allylic selenides in the presence of various amine nucleophiles provides synthetic access to a variety of allylic amine derivatives.The stereochemical outcome of these reactions has been investigated, and is consistent with a -sigmatropic rearrangement mechanism.Several D-α-amino acids and racemic β,γ-unsaturated α-amino acids were prepared in this manner.A variant of this process employing an achiral allylic selenide and chiral amide afforded protected allylic amines in low diastereoisomeric excess.
- Shea, Regan G.,Fitzner, Jeffrey N.,Fankhauser, John E.,Spaltenstein, Andreas,Carpino, Philip A.,et al.
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p. 5243 - 5252
(2007/10/02)
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- TOTAL SYNTHESIS OF SYLVAMIDE, A PIPER ALKAMIDE
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Key Word Index - Piper sylvaticum; Piperaceae; alkamide; sylvamide; N-isobutyl-4,5-dihydroxy-2(E)-decenamide. The structure, N-isobutyl-4,5-dihydroxy-2(E)-decenamide, for sylvamide is confirmed by its total synthesis.The erythro stereochemistry is also established by comparison of the properties of the natural and synthetic samples.
- Banerji, Avijit,Pal, Sudhir C.
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p. 1028 - 1030
(2007/10/02)
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- The Synthesis of a Cyclopropane Amino Acid, trans-α-(Carboxycyclopropyl)glycine, found in Ackee Seed
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trans-α-(Carboxycyclopropyl)glycine, a constituent of ackee seed (Blighia sapida), has been synthesized via the key intermediate ethyl (E)-4,4-diethoxybut-2-enoate.
- Landor, Stephen R.,Landor, Phyllis, D.,Kalli, Michael
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p. 2921 - 2926
(2007/10/02)
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