- Asymmetric synthesis of dihydrocarbazoles through a Friedel-Crafts alkylation/annulation sequential reaction of indoles
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An enantioselective tandem Friedel-Crafts alkylation/annulation of indoles with diazoacetoacetate enones is realized in one pot. A series of dihydrocarbazoles were obtained in moderate yields with good to excellent ee values by using a RhII/ScIII dual-metallic catalyst system. Control experiments revealed that ScIII is critical to both the alkylation and annulation.
- Hu, Linfeng,Cao, Weidi,Wang, Kaixuan,Liu, Xiaohua,Feng, Xiaoming
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supporting information
p. 13138 - 13141
(2021/12/16)
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- Iodine-Mediated Domino Cyclization for One-Pot Synthesis of Indolizine-Fused Chromones via Metal-Free sp3C-H Functionalization
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An efficient method for the synthesis of new indolizine-fused chromones has been accomplished from ethyl (E)-3-(2-acetylphenoxy)acrylates and pyridines in a "one-pot"manner. Facile operation in open-air, metal-free, and mild conditions renders this protocol particularly practical and attractive. Moreover, this method can simultaneously construct two molecular fragments of chromone and indolizine. Scale-up experiment and the construction of natural products further prove the practicability of this strategy.
- Fan, Wei-Yu,Feng, Meng-Lin,Gao, Jing-Jing,Wang, Zhuo,Wu, Rui-Xue,Yang, Kai-Rui,Zhang, Han,Zhang, Xiang-Jin,Zhu, Wei,Zhu, Yan-Ping
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- Environment-friendly preparation method of propiolic acid derivatives
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The invention discloses an environment-friendly preparation method of propiolic acid derivatives. The preparation method comprises the following steps: (1) with 2,3-dibromosuccinic acid as a raw material, generating a butynedioic acid salt under alkaline conditions; (2) under an acidic condition, carrying out high-temperature decarboxylation to obtain propiolic acid; and (3) adding corresponding methanol or ethanol into propiolic acid in an extraction solvent, and preparing high-yield propiolate under acidic catalytic conditions under the condition that trimethyl orthoformate or triethyl orthoformate participates in dehydration. In the invention, the propiolic acid preparation method is friendly to environment and high in safety coefficient; and the method provided by the invention can beused for preparing methyl propiolate and ethyl propiolate, and has the advantages of small alcohol consumption, thorough reaction, high yield and easiness in separation.
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Paragraph 0035-0038
(2020/02/14)
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- One-pot mild and efficient synthesis of [1,3]thiazino[3,2-: A] indol-4-ones and their anti-proliferative activity
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A base mediated environmentally benign one-pot efficient methodology has been developed for the synthesis of [1,3]thiazino[3,2-a]indol-4-ones using indoline-2-thiones and propiolate esters in aqueous medium. The conjugate addition of thiones first results in ethyl (3-(indol-2-yl)thio)acrylates in situ, which subsequently undergoes intramolecular cyclization to produce indole-fused thiazin-4-ones in good to excellent yields. The cytotoxic screening of the synthesized compounds using MTT assay revealed the anti-proliferative nature of these frameworks against triple negative breast cancer cell lines with the highest activity emanating from 4H-[1,3]thiazino[3,2-a]indol-4-one and 8-methyl-2-propyl-4H-[1,3]thiazino[3,2-a]indol-4-one compounds.
- Rhodes, Steven,Short, Spencer,Sharma, Sidhika,Kaur, Ramneet,Jha, Mukund
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supporting information
p. 3914 - 3920
(2019/04/30)
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- Production Of Terephthalic Acid Via Reductive Coupling Of Propiolic Acid Or Propiolic Acid Derivatives
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A method of making terephthalic acid via reductive coupling of two molecules of propiolic acid or propiolic acid derivatives is presented. The reductive coupling can be catalyzed by compounds comprising metals, and propiolic acid or propiolic acid derivatives can be produced from acetylene and carbon dioxide. At least 4 of the 8 carbons in the terephthalic acid are non-fossil-derived.
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Paragraph 0035
(2016/10/04)
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- Tandem Claisen Rearrangement/6-endo Cyclization Approach to Allylated and Prenylated Chromones
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Allyl, dimethylallyl and prenyl ethers derived from o-acylphenols reacted upon microwave irradiation to form C-allylated or -prenylated chromone derivatives, depending on the substitution pattern of the arene and the allyl substituent. The reaction proceeds through a tandem Claisen rearrangement and 6-endo-trig or 6-endo-dig cyclization sequence. For prenyl ethers, the tandem sequence can be extended by a Cope rearrangement to furnish 6-prenylchromones. The method is potentially useful for the synthesis of natural products and drugs.
- Schmidt, Bernd,Riemer, Martin,Schilde, Uwe
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supporting information
p. 7602 - 7611
(2016/01/25)
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- Gold-catalyzed formal [4π+2π]-cycloadditions of tert-butyl propiolates with aldehydes and ketones to form 4H-1,3-dioxine derivatives
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Gold-catalyzed formal hetero-[4π+2π] cycloadditions of tert-butyl propiolates with carbonyl compounds proceeded efficiently to yield 4H-1,3-dioxine derivatives over a wide scope of substrates. With acetone as a promoter, gold-catalyzed cycloadditions of these propiolate derivatives with enol ethers led to the formation of atypical [4+2]-cycloadducts with skeletal rearrangement.
- Karad, Somnath Narayan,Chung, Wei-Kang,Liu, Rai-Shung
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supporting information
p. 13004 - 13007
(2015/08/06)
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- Copper(II)-catalyzed silylation of activated alkynes in water: Diastereodivergent access to E- or Z-β-silyl-α,β-unsaturated carbonyl and carboxyl compounds
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Copper(II)-catalyzed silylation of substituted alkynylcarbonyl compounds was investigated. Through the activation of Me2PhSiBpin in water at room temperature and open atmosphere, vinylsilanes conjugated to carbonyl groups are synthesized in high yield. A surprising diastereodivergent access to olefin geometry was discovered using a silyl conjugate addition strategy: aldehydes and ketones were Z selective while esters and amides were exclusively transformed into the E products. Dial a diastereomer: The title reaction proceeds through the activation of Me2PhSiBpin in water at room temperature and open atmosphere to produce high yields of vinylsilanes conjugated to carbonyl groups. A surprising diastereodivergent access to olefin geometry was discovered using this silyl conjugate addition strategy: aldehydes were Z selective while esters and amides exclusively delivered the E-configured products.
- Calderone, Joseph A.,Santos, Webster L.
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supporting information
p. 4154 - 4158
(2014/05/06)
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- Aliphatic amino acid biosynthesis inhibitors and a method of synthesizing the same
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The embodiments herein provide a composition and a method of synthesizing a composition comprising an aliphatic amino acid biosynthesis inhibitor having an antifungal activity. The composition comprises 2-oxo-2H-chromen-7-yl propiolate, diethyl-hex-2-en-4-yne-dioate and dinonyl-hex-2-en-4-yne-dioate. The composition inhibits a biosynthesis of an aliphatic amino acid in a fungal biological system. The aliphatic amino acid is selected from a group consisting of leucine, isoleucine and valine. The composition is used with a concentration of 0-200 μg/ml. The method comprises mixing solutions of dicyclohexylcarbodiimide (DCC) and Dimethylaminopyridine (DMAP) with alcohol, acetylene carboxylic acid and dichloromethane to obtain a mixture which is stirred filtered and washed with ether. The solvents are evaporated to obtain a residue that is dissolved in dichloromethane and stirred with a catalyst. The extra solvents are evaporated to obtain the derivative compound and purified by silica gel column chromatography.
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Paragraph 0108-0109
(2013/11/05)
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- Stereoselective synthesis of hex-2-(E)-en-4-yn-1,6-dioates and E,Z-muconic acid diesters via organo-catalyzed self-coupling of propiolates
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Alkyl propiolate couples with itself in the presence of catalytic DABCO under very mild conditions to provide a quantitative yield of E-hex-2-en-4-yne dioates. Hydrogenation of these enyne dioates using Lindlar catalyst provides the corresponding E,Z-diene dioate, a common structural motif found in an array of natural products.
- Ramachandran, P. Veeraraghavan,Rudd, Michael T.,Reddy, M. Venkat Ram
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p. 2547 - 2549
(2007/10/03)
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- Synthesis and characterization of coordinatively unsaturated alkynyl- and aryl-cobalt complexes with 15 valence electrons, TpiPr2Co-R, bearing the hydrotris(3,5-diisopropylpyrazolyl)borato ligand (TpiPr2)
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Coordinatively unsaturated 15e alkynyl- (TpiPr2Co-C≡C-R) and aryl-cobalt complexes (TpiPr2Co-aryl) bearing the hydrotris(3,5-diisopropylpyrazolyl)borato ligand (TpiPr2) are prepared by dehydrative condensation of the hydroxo complex [TpiPr2Co(μ-OH)2]2 with 1-alkyne and arylation of the chloro complex TpiPr2Co-Cl with Grignard reagents, respectively. Spectroscopic and crystallographic analyses reveal the apparent C3-symmetrical tetrahedral structures with high-spin electronic configuration (S = 3/2), which should result from the property of the TpiPr2 ligand as a tetrahedral enforcer. The TpiPr2Co and hydrocarbyl fragments, are connected dominantly through σ-bonding interaction, and π-interaction including back-donation is not significant as revealed by EHMO calculations. The Co-C bonds are so polarized as to be readily protonated even by moisture to give the corresponding hydrocarbons, but the reactivity toward unsaturated hydrocarbons turns out to be sluggish. TpiPr2Co-C≡C-COOMe is found to catalyze a rare example of specific linear trimerization of methyl propiolate to give (E,E)-MeOOC(H)C=CH-CH=C(COOMe)-C≡C-COOMe.
- Yoshimitsu, Shin-Ichi,Hikichi, Shiro,Akita, Munetaka
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p. 3762 - 3773
(2008/10/08)
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- Alkynyl containing hydroxamic acid compounds as matrix metalloproteinase/tace inhibitors
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Compounds of the formula: useful in the treatment of arthritis, tumor metastasis, tissue ulceration, abnormal wound healing, periodontal disease, bone disease, diabetes (insulin resistance) and HIV infection.
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- Acetylenic aryl sulfonamide and phosphinic acid amide hydroxamic acid TACE inhibitors
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Hydroxamic acids having the formula are useful in treating disease conditions mediated by TNF-α, such as rheumatoid arthritis, osteoarthritis, sepsis, AIDS, ulcerative colitis, multiple sclerosis, Crohn's disease and degenerative cartilage loss.
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- Synthesis of polyalkylphenyl prop-2-ynoates and their flash vacuum pyrolysis to polyalkylcyclohepta[b]furan-2(2H)-ones
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A new method for the smooth and highly efficient preparation of polyalkylated aryl propiolates has been developed. It is based on the formation of the corresponding aryl carbonochloridates (cf Scheme 1 and Table 1) that react with sodium (or lithium) propiolate in THF at 25-65°, with intermediate generation of the mixed anhydrides of the arylcarbonic acids and prop-2-ynoic acid, which then decompose almost quantitatively into CO2 and the aryl propiolates (cf. Scheme 11). This procedure is superior to the transformation of propynoic acid into its difficult-to-handle acid chloride, which is then reacted with sodium (or lithium) arenolates. A number of the polyalkylated aryl propiolates were subjected to flash vacuum pyrolysis (FVP) at 600-650°and 10-2 Torr which led to the formation of the corresponding cyclohepta[b]furan-2(2H)-ones in average yields of 25-45% (cf. Scheme 14). It has further been found in pilot experiments that the polyalkylated cyclohepta[b]furan-2(2H)-ones react with 1-(pyrrolidin-1-yl)cyclohexene in toluene at 120-130°to yield the corresponding 1,2,3,4- tetrahydrobenz[a]azulenes, which become, with the growing number of Me groups at the seven-membered ring, more and more sensitive to oxidative destruction by air (cf. Scheme 15).
- Nagel, Matthias,Hansen, Hans-Juergen
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p. 1022 - 1048
(2007/10/03)
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- Free-radical addition of 2-(perfluoroalkyl)ethanethiols to alkenes, alkadienes, cycloalkenes, alkynes and vinyl monomers
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The free-radical addition of 2-(perfluoroalkyl)ethanethiols (RFCH2CH2SH) to alkenes, cycloalkenes, alkadienes and alkynes has been studied to determine: (1) the mode of reaction, i.e. the stereochemistry, regiochemistry and any skeletal changes: (2) the relative reactivity towards unsaturates of differing structures and classes as affected by the presence of the RF group; and (3) the influence of the reaction conditions on the rate of addition or selectivity for different products.Adducts from 2-(F-hexyl)ethanethiol (1) and alkenes have been obtained in high yield,but containing small amounts of regio isomers.For example compound 1 with 1-heptene gave 1-heptane (3, 96percent yield) as well as 2-heptane (4, O.61percent) and 3-heptane (5, 2.22percent). 1,6-Hexadiene and 1,7-octadiene gave chiefly linear adducts, i.e.RFCH2CH2S(CH2)nCH=CH2 (7, n=4; or 12, n=6, respectively) and RFCH2CH2S(CH2)nSCH2CH2RF (8, n=6; or 14, n=8, respectively).A small amount (2-3percent) of cis- and trans-1-methyl-cyclohexane (13) isomers were present in 12.Compound 1 with 1,6-heptadiene gave 7--1-heptene (9), the bis adduct, 1,7-bis-heptane (11) and the cyclic adducts, cis- and trans-1-methal-2-methylcyclopentane (10).The relative amounts of cyclic isomers depended on the reactant ratio.Compound 1 added readily with free-radical initiation to vinyl monomers such as styrene and vinyl acetate, and to phenyl acetylene, propargyl acetate and ethyl propynoate.These new addition products are useful as models for further study.
- Brace, Neal O.
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p. 217 - 241
(2007/10/02)
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- N-Substituted aziridine-2-carboxylic acid derivatives and their immuno-stimulation compositions and methods
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A 2-cyanaziridine derivative of the formula STR1 wherein R' is a straight-chained or branched, saturated or mono- or polyunsaturated aliphatic hydrocarbon radical with up to 8 carbon atoms, which is substituted by an aromatic nitrogen-containing heterocyclic radical with 5 or 6 ring-members and 1, 2 or 3 nitrogen atoms optionally substituted by halogen, alkoxy with up to 8 carbon atoms, alkyl with up to 8 carbon atoms, hydroxyl, carbalkoxy with up to 9 carbon atoms, carbamoyl, dialkylamino the alkyl moieties of which having up to 8 carbon atoms, cycloalkylamino, the cycloalkyl moiety having 3-10 carbon atoms, acetylamino, nitro, cyano, acetyl, alkylthio with up to 8 carbon atoms, alkylsulphinyl with up to 8 carbon atoms, alkylsulphonyl with up to 8 carbon atoms, sulphamoyl, phenyl, trifluoromethyl, phenoxy, acetoxy or methylenedioxy; or a pharmacologically acceptable salt thereof, exhibits immune stimulating activity.
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- SYNTHESIS AND FRAGMENTATION-CONDENSATION REACTIONS OF 1,3-DIETHOXYCARBONYLALLYLIDENETRIPHENYLPHOSPHONIUM YLIDE
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Alkylidenephosphonium ylides with ethoxycarbonyl substituents in the α-position fragment in a retro-Michael fashion during condensation with aldehydes.
- Labuschagne, A. Johan H.,Schneider, David F.
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p. 4135 - 4138
(2007/10/02)
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- N-Substituted aziridine-2-carboxylic acid derivatives for immuno stimulation
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Aziridine-2-carboxylic acid derivatives of the formula STR1 wherein X is a carboxyl, nitrile, alkoxycarbonyl or carbamoyl group, and R and R1 are various organic radicals, or pharmacologically acceptable salts thereof, exhibit marked immunostimulant activity, especially in conjunction with added chemotherapeutic agents such as a penicillin, a cephalosporin, a nitrofuran or chloramphenicol. Those compounds are new where X is a cyano group or an alkoxycarbonyl radical and R1 is a hydrogen atom, but R' is not an unsubstituted alkyl radical or an alkyl radical substituted by hydroxyl, alkoxy, dialkylamino, phenyl, 4-chlorophenyl or 4-methoxyphenyl or a vinyl radical substituted by a phenyl or methyl radical, or a cycloalkyl radical, a phenyl a 4-chlorophenyl, a 4-methoxyphenyl, an s-triazinyl or a pyridinyl radical; or where X is a carbamoyl group and R1 is a hydrogen atom, R' is not an unsubstituted cyclohexyl, alkyl or benzyl radical; or where X is a cyano group or an alkoxycarbonyl radical and R1 is a phenyl radical, R' is not an isopropyl, cyclohexyl, phenyl, benzyl or p-chlorobenzyl radical; or where R1 is a methyl radical, R1 is not a benzyl, p-chloro- or p- methoxybenzyl radical.
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- Pyrazolo[1,5-c]quinazoline derivatives and related compounds
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Compounds are provided having the structure STR1 wherein R1 is hydrogen, alkyl of 1 to 3 carbons, 1-(hydroxyimino)alkyl, alkanoylamino, amino, or STR2 wherein alkyl in the above groups contains 1 to 4 carbons; R2 is 1-(hydroxyimino)alkyl, alkanoylamino, amino, STR3 hydrogen, lower alkyl or phenyl (optionally substituted by R4) wherein alkyl in the above groups contains 1 to 4 carbons; R3 is hydrogen, lower alkyl, benzyl or phenyl (optionally substituted with R4), dialkylaminoalkyl, hydroxyalkyl, STR4 (wherein R6 is hydrogen or alkyl, and R7 is alkyl); with the proviso that R1 or R2 is 1-(hydroxyimino)alkyl, alkanoylamino or amino, when R3 is hydrogen, lower alkyl, benzyl or phenyl; and R4 and R5 are the same or different and represent hydrogen, lower alkyl, lower alkoxy, alkanoyloxy, benzyloxy, hydroxy, halogen (Cl, Br and F), nitro and trifluoromethyl. The above compounds are useful as anti-allergy agents and antiinflammatory agents.
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