- Phytochemical study on American plants I. Two new phenol glucosides, together with known biflavones and diterpene, from leaves of Juniperus occidentalis Hook.
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Two new phenol glucosides termed juniperosides I (1) and II (2) were isolated, together with known two biflavones, cupressuflavone and amentoflavone and a diterpene, 3beta-hydroxy sandaracopimaric acid, from leaves of Juniperus occidentalis HOOK. (Cupress
- Nakanishi, Tsutomu,Inatomi, Yuka,Murata, Hiroko,Iida, Naoki,Inada, Akira,Lang, Frank A,Murata, Jin
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Read Online
- A theoretical study of the Duff reaction: Insights into its selectivity
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The Duff reaction is one of the most employed methods for the ortho-formylation of phenols; however, not much is truly known about its mechanism. Using DFT calculations, we disclose the first theoretical study regarding the selectivity-determining step of the reaction. We have found that this stage is governed by a hydrogen bond, that gives rise to a cyclohexa-2,4-dienone intermediate and establishes the position where the formylation will take place. These findings were evaluated by analysis of the reaction outcome of several non-symmetrically substituted phenols.
- Grimblat, Nicolás,Sarotti, Ariel M.,Kaufman, Teodoro S.,Simonetti, Sebastian O.
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Read Online
- Polymerizable Materials Based On Dimerizable Benzaldehyde Derivatives
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The present invention relates to polymerizable and photochemically crosslinkable compositions which contain at least one polymerizable benzaldehyde derivative according to general formula I and which are suitable as materials for technical and medical app
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- On-demand acid-gated fluorescence switch-on in photo-generated nanospheres
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Herein, we introduce a fast, additive-free, ambient temperature photochemical approach - utilising the novel Diels-Alder cycloaddition of a photo-activeortho-methylbenzaldehyde (oMBA) with a terminal alkyne - for preparing functional acid-sensitive proflu
- Barner, Leonie,Barner-Kowollik, Christopher,Cavalli, Federica,Delafresnaye, Laura,Feist, Florian,Hooker, Jordan P.
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p. 4986 - 4989
(2020/05/18)
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- Direct formylation of fluorine-containing aromatics with dichloromethyl alkyl ethers
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Formylations of fluorine-containing aromatic compounds with dichloromethyl alkyl ethers have been investigated. Dichloromethyl propyl ether and dichloromethyl butyl ether have been applied for the formylation of fluorine-containing anisoles to give the corresponding aldehydes in good yields. Application of these ethers is preferable to that of methyl ether, which is prepared from volatile methyl formate. Reaction of fluorine-containing phenols with these dichloromethyl alkyl ethers did not give salicylaldehyde derivatives, leading instead to corresponding aryl formates in high yields. A plausible mechanism is discussed.
- Warashina, Takuya,Matsuura, Daisuke,Kimura, Yoshikazu
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p. 587 - 593
(2019/07/22)
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- Protection-Group-Free Synthesis of Sequence-Defined Macromolecules via Precision λ-Orthogonal Photochemistry
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An advanced light-induced avenue to monodisperse sequence-defined linear macromolecules via a unique photochemical protocol is presented that does not require any protection-group chemistry. Starting from a symmetrical core unit, precision macromolecules
- Konrad, Waldemar,Fengler, Christian,Putwa, Sarrah,Barner-Kowollik, Christopher
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p. 7133 - 7137
(2019/04/26)
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- DUAL AGONISTS OF FXR AND PPARδ AND THEIR USES
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The present invention relates to small molecule compounds and their use as agonists of farnesoid X receptor (FXR) and/or peroxisome proliferator activated receptor delta (PPARδ). The present invention also relates to the use of said compounds in the treatment of metabolic diseases and respective methods of treatment.
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Page/Page column 38; 50
(2019/04/16)
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- Synthesis of Benzofuranones via Palladium-Catalyzed Intramolecular Alkoxycarbonylation of Alkenylphenols
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Herein, a new catalytic system to synthesize benzofuranones is reported. A palladium-catalyzed intramolecular alkoxycarbonylation is employed to generate 3-substituted-benzofuran-2(3H)-ones from alkenylphenols under mild reaction conditions, linked to an ex situ formation of CO from N-formylsaccharin. The carefully chosen catalytic system enables an efficient reaction with a novel functional group tolerance, despite the high polymerization tendency of the starting material.
- Hirschbeck, Vera,Fleischer, Ivana
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supporting information
p. 2854 - 2857
(2018/02/06)
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- A Combined Photochemical and Multicomponent Reaction Approach to Precision Oligomers
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We introduce the convergent synthesis of linear monodisperse sequence-defined oligomers through a unique approach, combining the Passerini three-component reaction (P-3CR) and a Diels–Alder (DA) reaction based on photocaged dienes. A set of oligomers is prepared resting on a Passerini linker unit carrying an isocyano group for chain extension by P-3CR and a maleimide moiety for photoenol conjugation enabling a modular approach for chain growth. Monodisperse oligomers are accessible in a stepwise fashion by switching between both reaction types. Employing sebacic acid as a core unit allows the synthesis of a library of symmetric sequence-defined oligomers. The oligomers consist of alternating P-3CR and photoblocks with molecular weights up to 3532.16 g mol?1, demonstrating the successful switching from P-3CR to photoenol conjugation. In-depth characterization was carried out including size-exclusion chromatography (SEC), high-resolution electrospray ionization mass spectrometry (ESI-MS) and NMR spectroscopy, evidencing the monodisperse nature of the precision oligomers.
- Konrad, Waldemar,Bloesser, Fabian R.,Wetzel, Katharina S.,Boukis, Andreas C.,Meier, Michael A. R.,Barner-Kowollik, Christopher
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p. 3413 - 3419
(2018/02/09)
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- Star polymer synthesis: Via λ-orthogonal photochemistry
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We introduce a light induced sequence enabling λ-orthogonal star polymer formation via an arms-first approach, based on an α,ω-functional polymer carrying tetrazole and o-methyl benzaldehyde moieties, which upon irradiation can readily undergo cycloaddition with a trifunctional maleimide core. Depending on the wavelength, the telechelic strand can be attached to the core at either photo-reactive end.
- Hiltebrandt, Kai,Kaupp, Michael,Molle, Edgar,Menzel, Jan P.,Blinco, James P.,Barner-Kowollik, Christopher
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p. 9426 - 9429
(2016/07/29)
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- Formylation of electron-rich aromatic rings mediated by dichloromethyl methyl ether and TiCl4: Scope and limitations
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Here the aromatic formylation mediated by TiCl4 and dichloromethyl methyl ether previously described by our group has been explored for a wide range of aromatic rings, including phenols, methoxy- and methylbenzenes, as an excellent way to produce aromatic aldehydes. Here we determine that the regioselectivity of this process is highly promoted by the coordination between the atoms present in the aromatic moiety and those in the metal core.
- Ramos-Tomillero, Iván,Paradís-Bas, Marta,De Pinho Ribeiro Moreira, Ibério,Bofill, Josep María,Nicolás, Ernesto,Albericio, Fernando
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supporting information
p. 5409 - 5422
(2015/05/13)
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- Aldehyde-Assisted Ruthenium(II)-Catalyzed C-H Oxygenations
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Versatile ruthenium(II) complexes allow for site-selective C-H oxygenations with weakly-coordinating aldehydes. The challenging C-H functionalizations proceed with high chemoselectivity by rate-determining C-H metalation. The new method features an ample substrate scope, which sets the stage for the step-economical preparation of various bioactive heterocycles.
- Yang, Fanzhi,Rauch, Karsten,Kettelhoit, Katharina,Ackermann, Lutz
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supporting information
p. 11285 - 11288
(2016/02/18)
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- Light-induced modular ligation of conventional RAFT polymers
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Making light work of RAFT conjugation: A non-activated RAFT agent at the end of RAFT polymers can readily be coupled with ortho-quinodimethanes (photoenols) in a photo-triggered Diels-Alder reaction under mild conditions without catalyst (see scheme). The
- Oehlenschlaeger, Kim K.,Mueller, Jan O.,Heine, Niklas B.,Glassner, Mathias,Guimard, Nathalie K.,Delaittre, Guillaume,Schmidt, Friedrich G.,Barner-Kowollik, Christopher
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p. 762 - 766
(2013/02/23)
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- Light induced DNA-protein conjugation
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DNA was modified with a photo-reactive caged diene allowing for the modification of dienophile containing proteins under mild irradiation conditions to afford fully functional DNA-protein conjugates.
- Bauer, Dennis M.,Rogge, Anita,Stolzer, Lukas,Barner-Kowollik, Christopher,Fruk, Ljiljana
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p. 8626 - 8628
(2013/09/23)
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- Adding spatial control to click chemistry: Phototriggered diels-alder surface (Bio)functionalization at ambient temperature
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A photoconjugation strategy based on light-triggered Diels-Alder addition of o-quinodimethanes is compatible with biomolecules and proceeds rapidly at ambient temperature without the need of a catalyst. Spatial control was confirmed by photopatterning of
- Pauloehrl, Thomas,Delaittre, Guillaume,Winkler, Volker,Welle, Alexander,Bruns, Michael,B?rner, Hans G.,Greiner, Alexandra M.,Bastmeyer, Martin,Barner-Kowollik, Christopher
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p. 1071 - 1074
(2012/03/11)
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- Insertion of arynes into the carbon-oxygen double bond of amides and its application into the sequential reactions
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The reaction of arynes, generated from ortho-(trimethylsilyl)aryl triflates, with the CO bond of formamides gave salicylaldehyde derivatives via the formation of formal [2+2] adducts. The sequential transformation of arynes into ortho-disubstituted arenes, o-aminoalkylphenols or o-hydroxyalkylphenols, was achieved by one-pot procedure using dialkylzincs.
- Yoshioka, Eito,Miyabe, Hideto
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experimental part
p. 179 - 189
(2012/02/15)
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- Regio- and enantioselective intermolecular hydroacylation: Substrate-directed addition of salicylaldehydes to homoallylic sulfides
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We report a Rh-catalyzed, regio- and enantioselective intermolecular olefin hydroacylation under mild conditions. Hydroacylations between homoallylic sulfides, containing a substrate-bound directing group, and salicylaldehyde derivatives occur in the presence of a spiro-phosphoramidite ligand, (R)-SIPHOS-PE, to give α-branched ketones in >20:1 selectivity and up to 97% ee. Our conditions are also applicable to the asymmetric intermolecular hydroacylation of 1,2-disubstituted olefins.
- Coulter, Matthew M.,Kou, Kevin G. M.,Galligan, Baye,Dong, Vy M.
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p. 16330 - 16333
(2011/02/23)
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- Expeditious synthesis of benzopyrans via lewis acid-catalyzed C-H functionalization: Remarkable enhancement of reactivity by an ortho substituent
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An expeditious construction of a benzopyran skeleton via Lewis acid-catalyzed C-H functionalization was achieved. In this process, a [1,5] hydride shift and 6-endo cyclization successively occurred to give benzopyrans. The presence of substituents ortho to the alkoxy group significantly enhanced the reactivity, affording the desired compounds in excellent chemical yields with short reaction times.
- Mori, Keiji,Kawasaki, Taro,Sueoka, Shosaku,Akiyama, Takahiko
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supporting information; experimental part
p. 1732 - 1735
(2010/09/05)
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- The synthesis of 2-hydroxymethyl derivatives of phenols
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2-Hydroxymethylphenols have been prepared in good yield by reduction with sodium borohydride of the precursor aldehydes, obtained regiospecifically from reaction of phenols with paraformaldehyde in toluene containing stannic chloride and tri-n-butylamine. By contrast, reaction of phenols with either paraformaldehyde under anhydrous conditions or with aqueous formaldehyde results in formation of both the hydroxymethyl and the bishydroxymethyl derivatives. Cyclic acetals of the precursor aldehydes are readily accessible.
- Payne, Peter,Tyman, John H. P.,Mehet, Satinder K.,Ninagawa, Akira
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p. 402 - 405
(2007/10/03)
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- Non-metallocene compounds, method for the production thereof and use of the same for the polymerisation of olefins
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The invention relates to a method for producing special transition metal compounds, to novel transition metal compounds and to the use of the same for the polymerisation of olefins.
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- BENZOPYRAN COMPOUNDS USEFUL FOR TREATING INFLAMMATORY CONDITIONS
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The subject invention concerns methods and compounds that have utility in the treatment of a condition associated with cyclooxygenase-2 mediated disorders. Compounds of particular interest are benzopyrans and their analogs defined by formula (1). Wherein Z, X, R1, R2, R3, and R4 are as described in specification.
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- CHROMENE DERIVATIVES AS ANTI-INFLAMMATORY AGENTS
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The subject invention concerns methods and compounds that have utility in the treatment of a condition associated with cyclooxygenase-2 mediated disorders. Compounds of particular interest are benzopyrans and their analogs defined by formula (I). Wherein Z, X, R1, R2, R3, and R4 are as described in the specification.
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- Convenient Method for the ortho-Formylation of Phenols
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Phenolic derivatives are formylated selectively ortho to the hydroxy group by paraformaldehyde with magnesium dichloride-triethylamine as base. With alkyl-substituted phenols excellent yields of the corresponding salicylaldehyde derivatives were obtained. Similar results were obtained with chloro-substituted phenols and with 3- and 4-methoxyphenol, while 2-methoxyphenol was unreactive. A good yield of methyl 3-formyl-4-hydroxybenzoate was obtained by this method as well, but generally phenols with electron-attracting groups reacted sluggishly; the long reaction times required caused the formation of by-products, particularly MOM-derivatives of the phenols.
- Hofslokken, Nini U.,Skattebol, Lars
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p. 258 - 262
(2007/10/03)
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- Facile Synthesis of 2-Hydroxy-6-methylbenzaldehyde, an Alarm and Sex Pheromone Component of Astigmatid Mites
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2-Hydroxy-6-methylbenzaldehyde (5) is a component of astigmatid mites, functioning as the alarm and sex pheromones, and the establishment of its convenient synthesis is prerequisite and of vital importance to develop applications of these pheromones for p
- Noguchi, Satoshi,Mori, Naoki,Kuwahara, Yasumasa,Sato, Masashi
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p. 1546 - 1547
(2007/10/03)
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- A facile synthesis of [14C]enadoline [(5R)-(5α,7α,8β)]-N-methyl-N-[7-(1-pyrrolidinyl)-1-oxospiro[4,5] dec-8-yl]-4-benzofuranacetamide
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4-Chloromethylbenzofuran (10) was synthesized from 2,3-dimethylanisole in 7 steps. The corresponding Grignard reagent prepared from magnesium anthracene complex reacts with 14CO2, SOCl2, and PD130812 successively to give [
- Pu,Scripko,Huang
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p. 1183 - 1191
(2007/10/03)
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- Magnesium-mediated ortho-Specific Formylation and Formaldoximation of Phenols
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Deprotonation of phenols using magnesium methoxide, followed by distillative removal of free methanol and addition of paraformaldehyde results in ortho-specific magnesium mediated formylation to give the corresponding salicyladehyde magnesium salts, from which the salicylaldehydes can be isolated by acidic work-up.Addition of aq. hydroxylamine sulfate to the salicylaldehyde magnesium salt, in place of the acid work-up, gives the corresponding salicylaldoximes.
- Aldred, Robert,Johnston, Robert,Levin, Daniel,Neilan, James
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p. 1823 - 1832
(2007/10/02)
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- Pseudoguaianolides from Intramolecular Cycloadditions of Aryl Diazoketones: Synthesis of (+/-)-Confertin and an Approach to the Synthesis of (+/-)-Damsin
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Rhodium(II) mandelate-catalysed cyclisation of α-diazoketones derived from 3-arylpropionic acids produces bicyclodecatrienones, one of which has been used to synthesise an advanced (+/-)-confertin intermediate in six stages and 20percent overall yield.The possibility of constructing intermediates for the synthesis of damsin-like pseudoguaianolides via catalysed diazoketone cyclisation is also examined and methods for the construction of polyfunctional 3-arylpropionic acids suitable for use as damsin precursors are presented.
- Kennedy, Michael,McKervey, M. Anthony
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p. 2565 - 2574
(2007/10/02)
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- Synthesis of Gerberinol-I
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The synthesis of 4-hydroxy-5-methylcoumarin (II) is described.The compound (II) affords gerberinol-I (I) on treatment with formaldehyde.The synthetic sample of I is identical (m.m.p. and co-IR) with an authentic I.
- Chatterjea, J. N.,Singh, K. R. R. P.,Jha, I. S.,Prasad, Y.,Shaw, S. C.
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p. 796 - 798
(2007/10/02)
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- Selective Syntheses Using Cyclodextrin as Catalyst. 1. Control of Orientation in the Attack of Dichlorocarbene at Phenolates
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4-Hydroxybenzaldehydes, 2,4-dihydroxybenzaldehyde, and 4-(dichloromethyl)-2,5-cyclohexadienones were synthesized in virtually 100percent selectivities and high yields from the corresponding phenols and chloroform in alkaline aqueous solutions by using α- or β-cyclodextrin (α- or β-CD) as catalyst.The regulation of the molar ratio of chloroform to CD below unity throughout the reaction time, by controlling the rate of addition of chloroform, was definitely required to attain high selectivity.Under these conditions, dichlorocarbene, prepared in situ from chloroform and sodium hydroxide, attacked overwhelmingly at the para carbon of phenols with almost perfect suppression of the reaction at the ortho carbon.The structure of the ternary molecular complex composed of β-CD, chloroform, and phenol, formed in the reaction mixture for the selective synthesis of 4-hydroxybenzaldehyde, was determined by NMR spectroscopy.The selective catalysis by CDs was attributed to the regulation of molecular conformation of phenols with respect to chloroform, and thus to dichlorocarbene, in the ternary complex.
- Komiyama, Makoto,Hirai, Hidefumi
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p. 2018 - 2021
(2007/10/02)
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- Process of preparing hexahydropyrimidines
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This invention relates to hexahydropyrimidines (HHP) of the formula STR1 where R' is a substituted group and R is hydrogen or a substituted group; the process of preparing and the uses therefor, particularly as deterioration inhibitors in hydrocarbon fuels.
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- Selective Reactions between Phenols and Formaldehyde. A Novel Route to Salicylaldehydes
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Treatment of phenols (1) with 2 mol equiv. of paraformaldehyde in aprotic and poorly electron-donating solvents in the presence of selected metal halides coupled with suitable bases produces salicylaldehydes (3) in high yields.The route is highly selective for ortho-formylation and also specific towards monoformylation.The crucial role of added bases is emphasized.
- Casiraghi, Giovanni,Casnati, Giuseppe,Puglia, Giuseppe,Sartori, Giovanni,Terenghi, Giuliana
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p. 1862 - 1865
(2007/10/02)
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