WO2011098375A2 - Verfahren zur allylierung und vinylierung von aryl-, heteroaryl-, alkyl- und alkenylhalogeniden unter übergangsmetallkatalyse - Google Patents
Verfahren zur allylierung und vinylierung von aryl-, heteroaryl-, alkyl- und alkenylhalogeniden unter übergangsmetallkatalyse Download PDFInfo
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- WO2011098375A2 WO2011098375A2 PCT/EP2011/051390 EP2011051390W WO2011098375A2 WO 2011098375 A2 WO2011098375 A2 WO 2011098375A2 EP 2011051390 W EP2011051390 W EP 2011051390W WO 2011098375 A2 WO2011098375 A2 WO 2011098375A2
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- HTDQSWDEWGSAMN-UHFFFAOYSA-N COc1ccccc1Br Chemical compound COc1ccccc1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/04—Preparation of carboxylic acid nitriles by reaction of cyanogen halides, e.g. ClCN, with organic compounds
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/04—Substitution
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B49/00—Grignard reactions
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
- C07C1/30—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by splitting-off the elements of hydrogen halide from a single molecule
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
- C07C1/326—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being a magnesium atom
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/2632—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions involving an organo-magnesium compound, e.g. Grignard synthesis
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/128—Compounds comprising a halogen and an iron group metal or a platinum group metal
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes
Definitions
- the invention relates to a process for the preparation of functionalized aryl, heteroaryl, alkenyl or alkyl compounds, by a transition metal-catalyzed cross-coupling reaction of an optionally substituted aryl, heteroaryl, alkenyl or alkylmagnesium compound with an optionally substituted allyl carboxylate, allyl carbonate, vinyl carboxylate or Vinyl carbonate, wherein the formation of Organomagnesiumverbindmig from a halide may optionally be carried out in situ in parallel to the coupling reaction. Transition-metal-catalyzed cross-coupling reactions are among the most important synthetic tools of modern organic chemistry.
- iron and also cobalt compounds have activity as catalysts in cross-coupling reactions.
- compounds of iron are available due to its property as a base metal at very low prices and thereby toxicologically and legally abwassserrechtiich harmless. Therefore, these compounds are preferable to the expensive palladium, the toxic and environmentally hazardous nickel and the environmentally hazardous copper as catalyst systems.
- iron salts can catalyze the cross-coupling of vinyl halides with alkylgrignard compounds (Koc et al., J. Am. Chem. Soc., 1971, 1487).
- the present invention solves this problem by providing a process comprising organomagnesium compounds derived from aryl, heiroaryl, alkyl and alkenyl halides, which may optionally be prepared in the presence of the allylic or vinylic coupling component, catalysed by iron complexes with allyl and vinyl carboxylates Coupling allyl and vinyl carbonates, while preserving the typical gentle conditions of iron catalysis.
- the substrate scope of the iron-catalyzed coupling has been extended considerably, since vinyl esters of aldehydes and ketones by enolization and acylation and allyl esters of allylic alcohols are very readily available.
- the invention therefore provides a process for the preparation of organic compounds of the general formula (I) - -
- R is an optionally mono- or polysubstituted aryl, heteroaryl, alkenyl or alkyl radical, and
- R ' is a vinyl or alkyl radical of general formula 11 (a) or 11 (b),
- q are the same or different groups other than H.
- X is fluorine, chlorine, bromine or iodine
- R has the meaning given for formula (I), to an organomagnesium compound of general formula (III)
- X is an anion having the meaning given for formula (II),
- M is a monovalent cation
- Y is a monovalent anion
- n is either 0 or n is 1, 2, 3, 4,
- n 1, 2, 3, 4, 5 or 6
- k 0, 1, 2, 3 or 4,
- R ' has the meaning given for formula (I) and is bonded to the oxygen atom in the allyl or vinyl position
- R '' is an optionally substituted Alkyk alkoxy, aryl, aryloxy, heteroaryl or the heteroaryloxy group, characterized in that the reaction of (III) with (IV), optionally also the step of (II ) to (III) in the presence
- the organomagnesium compound (III) can be prepared in a manner familiar to the person skilled in the art, for example by Grignard reaction of the compound (II) with elemental magnesium, under suitable conditions also by halogen metal exchange or deprotonation, optionally with the addition of auxiliaries such as Lithium chloride, or by transmetallation of other organometallic compounds, eg organolithium compounds, with suitable magnesium compounds, for example magnesium salts or Grignard compounds.
- organomagnesium compounds (III) are 4-tolylmagnesium chloride, undecylmagnesium bromide, bis (4-tolyl) -magnesium, bis (4-methoxyphenyl) -magnesium-lithium chloride complex, 2-methoxyphenyl-magnesium chloride-lithium chloride complex, lithium tributyl magnesiate, lithium dibutyl (3-tolyl) magnesiate or lithium tris (thiophen-2-yl) magnesiate.
- the radical R in the formulas (I), (II) and (III) it Bandelt is an optionally substituted (C -C) alkyl, (C 2 -C] 0) alkenyl, (C 6 -C 24) - Aryl radical or heteroaryl radical, wherein the heteroaromatic radical is a five-, six- or seven-membered ring having one or more nitrogen, phosphorus, oxygen or sulfur atoms in the ring.
- Aromatic, heteroaromatic and / or cycloaliphatic rings may optionally be fused to ring-shaped radicals.
- Examples of preferred aromatic radicals R are optionally mono- or polysubstituted phenyl-naphthyl, anthracenyl or phenanthryl radicals.
- Examples of preferred heteroaromatic radicals are optionally mono- or polysubstituted pyridyl, pyrimidyl, pyrazinyl, furyl, thiophenyl, oxazolyl, thiazolyl or pyrrolyl radicals.
- Preferred alkenyl radicals are optionally mono- or polysubstituted vinyl radicals.
- Preferred alkylic radicals are optionally monosubstituted or polysubstituted, open-chain, cyclic, straight-chain or branched alkyl radicals, in particular C 1 -C 5 -alkyl radicals.
- the alkenyl, alkyl, aromatic or heteroaromatic radical R may optionally bear one or more substituents which are independent of each other (C 6 -C] 8) - cycloalkyl, (CC ls) alkenyl, (C 4 -C 1g) cycloalkenyl, (C 4 -C 18) -Alkinyi, (C 4 -C 18) aryl, 0- [(C 4 -C 18) - alkyl], 0 - [(C 4 -C lg) -aryl], 0-Si [(C 4 -C 18) -alkyl] tJ [C 4 -C S)!
- Examples of preferred aromatic radicals R are 2-tolyl, 4-anisyl, 2-naphthyl, 4,4'-biphenyl, 3-tert-butoxycarbonylphenyl, 3,4- ⁇ 2,2-difluoromethylenedioxy) phenyl, Pentafluorophenyl or 2-Decalinylreste.
- Examples of preferred heteroaromatic radicals R are 4-trifluoromethylpyridyl, 4-quinolinyl, 3-memoxythiophen-2-yl, 4- (2,2-ethylenedioxy) memyl-furyl radicals.
- Examples of preferred vinylic radicals R are 2-methylprop-1-enyl, 3-styryl, cyclohex-1-enyl, 2-chlorobut-1-enyl, 3-squalenyl or 2-but-2-ene yl radicals.
- Examples of alkyl radicals are isopropyl, 1-butyl, 2-butyl, cyclohexyl, 4-methoxycyclohexyl or perfluorobutyl radicals.
- the allylic or vinylic radical R 'in formula (I) and formula (IV) may optionally carry one or more substituents Q which are independently (C 4 -C 18 ) -alkyl, (C -C 18 ) -cycloalkyl, (C 4 -C 18 ) alkenyl, (C 4 -C 18 ) cycloalkenyl, (C 4 -C ] g ) alkynyl, (C 8 -C 8 ) aryl, O - [(C 4 -C 8 ) Alkyl], 0 - [(C 4 -C 18 ) -aryl], 0-Si [(C 4 -C 18 ) -alkyl] n [C 4 -C 18 ] -aryl] 3 .
- Examples of preferred allylic radicals R ' are linear, branched and cyclic, optionally substituted (C 3 -d 8 ) -l-alkene-3-yl from the group allyl, Crotyk methallyl, 1-methylallyl, cyclo-pent-l -en-3-yl and cyclohex-1-en-3-yl.
- Examples of preferred vinylic radicals R ' are linear, branched and cyclic, optionally substituted (C 3 -C 18 ) -l-alkene-1-yl from the group consisting of vinyl, 1-propenyl, 2-methyl-1-propenyl , Cyclopent-1-en-1-yl or cyclohex-1-en-1-yl.
- the process is carried out by reacting the halogen compounds of the formula (II) with magnesium turnings to the Grignard compound, then adding the catalytic amount of an iron or cobalt compound and then slowly dropping the allyl or vinyl compound of the formula (IV) and then from a period of 2 to 4 hours, the reaction mixture continues stirring.
- the purification of the resulting product usually follows by column chromatography on silica gel.
- the reaction with compounds of the formula (II) is preferably carried out from the group 4-bromoanisole, bromobenzene, 4-bromoveratrol, 4-bromotoluene, 4-bromoanisole, 2-bromotoluene and 4-tert -Butylbrombenzol.
- Crotyl acetate as the compound of the formula (IV) can preferably be reacted with compounds of the formula (II) from the group consisting of 4-bromoanisole and 1-bromo-4-tert-butylbenzene.
- the reaction with compounds of the formula (II) is preferably carried out from the group consisting of 1-bromo-4-chlorobenzene, 1-bromo-4-fluorobenzo, 1-bromo-2,4 -difluorobenzene, 2-bromoanisole, methyl 4-bromobenzoate, 4-bromoanisole, 1,3-dibromobenzene, 1,4-dibromo, 4-bromoveratrole, 4-bromoanisole, 4-bromotoluene, 4-tert-butylbromobenzene.
- the radical R "in formula (IV) may optionally bear one or more substituents which are independently (C 1 -C 18 ) -alkyl (C 1 -C 8 ) -cycloalkyl, (C 1 -C 6) -alkenyl, ( C, -Cig) - cycloalkenyl, (CC 18 ) alkynyl, (C r C, g ) -aryl, 0 - [(CC i8 ) -alkyl], 0 - [(CC 18 ) -aryl], 0-Si [(C d8) -alkyl] n [dC 18) -aryl] 3-n, OC (0) - [(dC, 8) -Alkyr], OC (0) - [(C] -C18) -aryl ], NH 2, NH [(C, -C 18) - alkyl], N [(CC lg) alkyl] 2, H [(
- radical R "in formula (IV) are methyl, ethyl, propyl, isopropyl or phenyl, methoxy, ethoxy, propoxy, isopropoxy or phenoxy radicals.
- Examples of compound (F7) are allyl acetate, crotyl propionate, methallyldodecanoate, cyclohex-1-en-3-ylbutanoate, allylmethyl carbonate, (hex-1-en-3-yl) phenyl carbonate and vinyl acetate, 1-propenyl acetate, 2-propenylmethyl carbonate, Cyclohex-1-en-1-ylpropionate.
- the catalysts used are preferably transition metal compounds of group VIIIB of the periodic table.
- Iron or cobalt compounds are particularly preferably used, most preferably iron compounds of any oxidation state, preferably the oxidation states +2 and +3, for example iron (II) chloride, iron (III) chloride, iron (II) acetylacetonate, iron (III ) acetylacetonate, iron (II) acetate, iron (III) acetate, iron (II) bromide, iron (III) bromide, iron (II) fluoride, iron (III) fluoride, iron (II) iodide, iron (HI ) iodide, iron (II) sulfate, iron (II) trifluoroacetate, iron (II) trifluoromethanesulfonate, iron (III) trifluoromethanesulfonate, iron (III) chloride TMEDA complex.
- the amount of catalyst used is preferably 0.01 to 100 mol%, particularly preferably 0.1 to 10 mol%, based on the
- nitrogen, oxygen and / or phosphorus-containing additives can be added in the process according to the invention.
- additives are preferably alkylamines, cycloalkylamines, alkyldiamines, cycloalkyldiamines, N-containing heterocycles, alkylamides, cyclic alkylamides, alkylimines, aniline derivatives, ureas, urethanes, nitrogen-containing heteroaromatics, dialkyl ethers, alkylaryl ethers, diaryl ethers, cyclic ethers, oligoethers, Polyethers, triarylphosphines, trialkylphosphines, aryldi- alkylphosphines, alkyldiarylphosphanes and bridged bisphosphanes.
- Particularly preferred additives are triethylamine, ethyldiisopropylamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylethylenediamine (TMEDA), 1,4-diazabicyclo [2.2.2] octane (DABCO), sparteine, N, N, N', N'-tetramethyldiaminomethane, 1,2-diaminocyclohexane (DACH), N-methyl-2-pyrrolidine (NMP), N, N-dimethylaniline, pyridine, phenanthroline, PEG (polyethylene glycol), DME (1,2-dimethoxyethane) Binaphthyldimethyl ether, 18-crown-6, triphenylphosphine, tri-n-butylphosphine, tri-tert-butylphosphane, dppf (l, -bis (diphenylphosphino) fer
- Chiral additives can also be used to achieve chiral induction in the coupling reaction, if applicable.
- the nitrogen, oxygen and / or phosphorus-containing additive is preferably used in an amount of 0 to 200 mol%, particularly preferably 0 to 150 mol%, based on the compounds (II).
- the process of the invention is usually carried out in dry aprotic polar solvents, which are preferably used in dry form.
- reaction temperature in the process of the invention is usually between -80 ° C and +100 ° C, preferably between -40 and +60 ° C,
- the process according to the invention makes it possible to react a large number of substituted and unsubstituted aryl, heteroaryl, alkyl and alkenyl halides with substituted and unsubstituted allyl and vinyl esters of substituted and unsubstituted carboxylic acids and carbonic acid.
- the linkage takes place predominantly on the C-axis of the allyl or vinyl ester which carries the ester function, ie. Isomerization and allyl shift take place, if at all, only to a lesser extent.
- the compounds prepared by the process according to the invention can be easily isolated and purified by conventional methods.
- the mixture was hydrolysed with 5 ml of saturated sodium bicarbonate solution and the mixture was extracted three times with 10 ml of ethyl acetate each time.
- the combined organic phases were dried over magnesium sulfate, concentrated and purified by column chromatography on silica gel (mobile phase cyclohexane-ethyl acetate).
- Example 54 Coupling of 4-bromoanisole with vinyl acetate
- Example 55 Coupling of bromotoluene with vinyl acetate as under domino iron catalysis g, TMEDA, FeCl 3 , THF
- Styrene was obtained in a yield of 42% d. Th.
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Abstract
Description
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Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2789079A CA2789079A1 (en) | 2010-02-09 | 2011-02-01 | Method for allylating and vinylating aryl, heteroaryl, alkyl, and alkene halogenides using transition metal catalysis |
BR112012019976A BR112012019976A2 (pt) | 2010-02-09 | 2011-02-01 | método para alilação e vinilação aril, heteroaril, alquil, e halogenetos de alqueno usando catálise de metal de transição. |
US13/577,278 US9309188B2 (en) | 2010-02-09 | 2011-02-01 | Method for allylating and vinylating aryl, heteroaryl, alkyl, and alkene halogenides using transition metal catalysis |
EP11702820A EP2534117A2 (de) | 2010-02-09 | 2011-02-01 | Verfahren zur allylierung und vinylierung von aryl-, heteroaryl-, alkyl- und alkenylhalogeniden unter übergangsmetallkatalyse |
MX2012009238A MX2012009238A (es) | 2010-02-09 | 2011-02-01 | Procedimiento para la alilar y vinilar halogenuros de arilo, heteroarilo, alquilo y alqueno usando catalisis de metales de transicion. |
JP2012552337A JP5540117B2 (ja) | 2010-02-09 | 2011-02-01 | 遷移金属触媒作用を用いてハロゲン化アリール、ハロゲン化ヘテロアリール、ハロゲン化アルキル、およびハロゲン化アルケンをアリル化およびビニル化する方法 |
AU2011214483A AU2011214483A1 (en) | 2010-02-09 | 2011-02-01 | Method for allylating and vinylating aryl, heteroaryl, alkyl, and alkene halogenides using transition metal catalysis |
KR1020127023324A KR101536041B1 (ko) | 2010-02-09 | 2011-02-01 | 전이 금속 촉매작용을 이용한 아릴, 헤테로아릴, 알킬 및 알켄 할로게나이드의 알릴화 및 비닐화 방법 |
Applications Claiming Priority (2)
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DE102010007226.5 | 2010-02-09 | ||
DE102010007226 | 2010-02-09 |
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WO2011098375A2 true WO2011098375A2 (de) | 2011-08-18 |
WO2011098375A3 WO2011098375A3 (de) | 2011-10-13 |
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PCT/EP2011/051390 WO2011098375A2 (de) | 2010-02-09 | 2011-02-01 | Verfahren zur allylierung und vinylierung von aryl-, heteroaryl-, alkyl- und alkenylhalogeniden unter übergangsmetallkatalyse |
Country Status (9)
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US (1) | US9309188B2 (de) |
EP (1) | EP2534117A2 (de) |
JP (1) | JP5540117B2 (de) |
KR (1) | KR101536041B1 (de) |
AU (1) | AU2011214483A1 (de) |
BR (1) | BR112012019976A2 (de) |
CA (1) | CA2789079A1 (de) |
MX (1) | MX2012009238A (de) |
WO (1) | WO2011098375A2 (de) |
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US9783476B2 (en) * | 2014-09-19 | 2017-10-10 | Toray Fine Chemicals Co., Ltd. | Method of producing 2′-trifluoromethyl group-substituted aromatic ketone |
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JP4423691B2 (ja) * | 1998-01-30 | 2010-03-03 | 東ソー株式会社 | スチレン誘導体の製造方法 |
US7026478B2 (en) * | 2002-05-10 | 2006-04-11 | Studiengesellschaft Kohle Mbh | Iron catalyzed cross coupling reactions of aromatic compounds |
EP1724248A4 (de) * | 2004-02-10 | 2008-02-20 | Japan Science & Tech Agency | Verfahren zur herstellung aromatischer verbindungen |
EP1582523A1 (de) * | 2004-04-02 | 2005-10-05 | Ludwig-Maximilians-Universität München | Verfahren zur Herstellung von Organomagnesiumverbindungen |
JP2007119379A (ja) * | 2005-10-26 | 2007-05-17 | Tosoh Corp | ジハロゲン化ビフェニル類の製造方法 |
EP1889849A1 (de) | 2006-07-18 | 2008-02-20 | Lonza Ag | Reaktionen vom Grignardtyp in Mikroreaktoren |
US8030520B2 (en) * | 2008-03-31 | 2011-10-04 | Saltigo Gmbh | Process for preparing organic compounds by a transition metal-catalysed cross-coupling reaction of an aryl-X, heteroaryl-X, cycloalkenyl-X or alkenyl-X compound with an alkyl, alkenyl, cycloalkyl or cycloalkenyl halide |
CN101318896B (zh) * | 2008-07-03 | 2011-02-16 | 浙江大学 | 合成顺式α-烯丙基-β,γ-不饱和羧酸酯的方法 |
JP5131772B2 (ja) * | 2008-10-31 | 2013-01-30 | 国立大学法人九州大学 | ビニル化合物の製造方法 |
CA2755147A1 (en) * | 2011-10-14 | 2013-04-14 | University Of Prince Edward Island | Iron bisphenolate complexes and methods of use and synthesis thereof |
EP2671866A1 (de) * | 2012-06-04 | 2013-12-11 | Saltigo GmbH | Verfahren zur Herstellung von Styrolderivaten |
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2011
- 2011-02-01 KR KR1020127023324A patent/KR101536041B1/ko not_active IP Right Cessation
- 2011-02-01 US US13/577,278 patent/US9309188B2/en not_active Expired - Fee Related
- 2011-02-01 BR BR112012019976A patent/BR112012019976A2/pt not_active IP Right Cessation
- 2011-02-01 CA CA2789079A patent/CA2789079A1/en not_active Abandoned
- 2011-02-01 EP EP11702820A patent/EP2534117A2/de not_active Withdrawn
- 2011-02-01 JP JP2012552337A patent/JP5540117B2/ja not_active Expired - Fee Related
- 2011-02-01 WO PCT/EP2011/051390 patent/WO2011098375A2/de active Application Filing
- 2011-02-01 MX MX2012009238A patent/MX2012009238A/es not_active Application Discontinuation
- 2011-02-01 AU AU2011214483A patent/AU2011214483A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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MX2012009238A (es) | 2012-12-05 |
KR101536041B1 (ko) | 2015-07-10 |
JP5540117B2 (ja) | 2014-07-02 |
EP2534117A2 (de) | 2012-12-19 |
AU2011214483A1 (en) | 2012-09-20 |
KR20120115577A (ko) | 2012-10-18 |
US9309188B2 (en) | 2016-04-12 |
JP2013518919A (ja) | 2013-05-23 |
WO2011098375A3 (de) | 2011-10-13 |
CA2789079A1 (en) | 2011-08-18 |
US20130184485A1 (en) | 2013-07-18 |
BR112012019976A2 (pt) | 2016-05-03 |
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