- Preparation method of 3-(3-oxo-2-pentyl) cyclopentyl dimethyl malonate
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The invention relates to a preparation method of 3-(3-oxo-2-pentyl) cyclopentyl dimethyl malonate. The preparation method of the 3-(3-oxo-2-pentyl) cyclopentyl dimethyl malonate comprises the following step: in the presence of a transition metal complex and a catalytic additive, reacting 2-pentyl-2-cyclopentenone with dimethyl malonate in a reaction solvent to obtain the 3-(3-oxo-2-pentyl) cyclopentyl dimethyl malonate. According to the preparation method provided by the invention, a sodium methoxide strong base catalyst is not needed, the generation of salt-containing wastewater is avoided, the method is environment-friendly and high in yield, and meanwhile, the recycling of the catalyst is realized.
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Paragraph 0063; 0067-0069; 0073-0075; 0079-0081; 0085-0087;
(2020/09/20)
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- Preparation method of methyl dihydrojasmonate
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The invention discloses an efficient synthesis method of methyl dihydrojasmonate. Under catalysis of homogeneous rhodium and organic nitric oxide, 1-heptyne and ethylene have Pauson-Khand reaction, 2-amyl-2-cyclopentenone is rapidly and efficiently obtained, and an intermediate is subjected to addition and decarboxylation by dimethyl malonate to obtain the methyl dihydrojasmonate. The efficient synthesis method mainly has the advantages that 1-heptyne and ethylene Pauson-Khand reaction yield is effectively improved by the aid of the organic nitric oxide, and usage of rhodium catalysts is reduced. Compared with a traditional methyl dihydrojasmonate production method, the method has the advantages that route steps are short, atom economy is high, the cost is low, and the method is suitable for scale production of the methyl dihydrojasmonate.
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- Method of manufacturing methylcyclopentanone deriv. (by machine translation)
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PROBLEM TO BE SOLVED: To provide an efficient method for producing a cyclopentanone derivative usable as an intermediate for a methyl (3-oxocyclopentyl)acetate derivative useful as a perfumery material.SOLUTION: The method for producing the cyclopentanone derivative expressed by general formula (III) comprises Michael addition reaction of a 2-cyclopenten-1-one derivative and an ester compound in the presence of a solid base catalyst containing a phosphazene base or a guanidine base. In the formula, Ris a 1-10C hydrocarbon group; Ris 1-4C alkyl; and Ris 1-4C alkyl or alkoxyl.
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- Further explorations into the synthesis of Dehydro-Hedione
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Dehydrohedione (DHH) 1 may be obtained in 20% overall yield by a Reformatsky reaction with enone methyl ether 3b, followed by acidic workup of the crude reaction mixture. Alternatively, epoxidation (3-chloroperbenzoic acid, CH2Cl2, 84% yield) of the tertiary allyl alcohol derivative 4 affords a 1: 2 mixture of 8a and 8b. The latter epoxy ester 8b may also be obtained stereoselectively either from 4 (tBuO2H, [Mo(CO)6], 1,2-dichloroethane, 70°, 62% yield; or tBuO2H, [VO(acac)2], decane, 20°, 92% yield), or from 5 (AcOMe, LiN(SiMe3)2, THF, -78°, 84-87%). BF3×Et2O-Catalyzed cascade rearrangement and OH elimination of 8a afford selectively DHH 1 in 88% yield. The cis disposition of the side chains of the weakly odoriferous hedione-like analogues 2b and 2c was maintained by means of either an epoxy or a cyclopropane moiety. Copyright
- Winter, Béat,Chapuis, Christian,Brauchli, Robert,De Saint Laumer, Jean-Yves
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p. 246 - 258
(2013/03/28)
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- METHOD FOR PRODUCING OF 2-ALKYL-2-CYCLOALKEN-1-ONE
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The present invention relates to [1] a process for producing a 2-alkyl-2-cycloalken-1-one represented by the following general formula (2), which includes the step of subjecting a 2-(1-hydroxyalkyl)cycloalkan-1-one to dehydration and isomerization in the co-existence of an acid and a platinum group metal catalyst, and [2] a process for producing an alkyl(3-oxo-alkylcycloalkyl)acetate which is useful as a perfume material, using the 2-alkyl-2-cycloalken-1-one: wherein n is an integer of 1 or 2; and R1 and R2 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms with the proviso that R1 and R2 may form a ring through a carbon atom adjacent thereto.
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- METHOD FOR PRODUCING OF 2-ALKYL-2-CYCLOALKEN-1-ONE
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The present invention relates to [1] a process for producing a 2-alkyl-2-cycloalken-1-one represented by the following general formula (2), which includes the step of subjecting a 2-(1-hydroxyalkyl)cycloalkan-1-one to dehydration and isomerization in the co-existence of an acid and a platinum group metal catalyst, and [2] a process for producing an alkyl(3-oxo-alkylcycloalkyl)acetate which is useful as a perfume material, using the 2-alkyl-2-cycloalken-1-one: wherein n is an integer of 1 or 2; and R1 and R2 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms with the proviso that R1 and R2 may form a ring through a carbon atom adjacent thereto.
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Page/Page column 14-15
(2011/01/12)
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- New jasmonate analogues as potential anti-inflammatory agents
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In an effort to develop new anti-inflammatory agents, methyl jasmonate analogues (2-20) were synthesized and evaluated for their inhibitory effects on the production of pro-inflammatory mediators (NO, IL-6, and TNF-α) in lipopolysaccharide (LPS)-activated RAW264.7 murine macrophage cells. The introduction of an enone functionality to the structure of a plant hormone (1) rendered the product (2) a significant anti-inflammatory activity. Analogues further derived from 2 (7, 9, 13, and 15) exhibited even more enhanced activity, and these compounds were much more potent than natural anti-inflammatory prostaglandins (PGA1, PGA2, and 15-deoxy-Δ12,14-PGJ2). Among them, compounds 9 and 15 showed the highest potency, while compounds 7 and 13 would be more desirable with respect to safety. This is the first study demonstrating the anti-inflammatory potential of jasmonate derivatives, and the present results suggest that α-haloenone jasmonates (7, 9, 13, and 15) may serve as potential anti-inflammatory leads.
- Dang, Hung The,Lee, Hye Ja,Yoo, Eun Sook,Hong, Jongki,Bao, Baoquan,Choi, Jae Sue,Jung, Jee H.
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experimental part
p. 10228 - 10235
(2009/04/10)
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- Highly selective hydrogenation of carbon-carbon multiple bonds catalyzed by the cation [(C6Me6)2Ru2(PPh 2)H2]+: Molecular structure of [(C 6Me6)2Ru2(PPh2)(CHCHPh)H] +, a possible intermediate in the case of phenylacetylene hydrogenation
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The dinuclear cation [(C6Me6)2Ru 2(PPh2)H2]+ (1) has been studied as the catalyst for the hydrogenation of carbon-carbon double and triple bonds. In particular, [1][BF4] turned out to be a highly selective hydrogenation catalyst for olefin functions in molecules also containing reducible carbonyl functions, such as acrolein, carvone, and methyljasmonate. The hypothesis of molecular catalysis by dinuclear ruthenium complexes is supported by catalyst-poisoning experiments, the absence of an induction period in the kinetics of cyclohexene hydrogenation, and the isolation and single-crystal X-ray structure analysis of the tetrafluoroborate salt of the cation [(C6Me6)2Ru2(PPh 2)-(CHCHPh)H]+ (2), which can be considered as an intermediate in the case of phenylacetylene hydrogenation. On the basis of these findings, a catalytic cycle is proposed which implies that substrate hydrogenation takes place at the intact diruthenium backbone, with the two ruthenium atoms acting cooperatively in the hydrogen-transfer process.
- Tschan, Mathieu J.-L.,Suess-Fink, Georg,Cherioux, Frederic,Therrien, Bruno
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p. 292 - 299
(2007/10/03)
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- Method of producing acetate derivative
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The present invention relates to a method of producing an acetate derivative represented by the formula (II) by demonocarboxylating dimalonate represented by the formula (I), wherein water is supplied while the concentration of water in a demonocarboxylating reaction solution is controlled to 0.4% by weight or less to run demonocarboxylation: wherein n denotes an integer of 1 or 2, R1 and R2 represent H, a C1-8 alkyl group or the like and R3 represents a C1-3 alkyl group.
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- Cycloalkanone composition
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The present invention relates to a cycloalkanone composition which contains cycloalkanone (1) in an amount of 70 wt% or more based on the composition, wherein the content of a dimer of a cycloalkanone represented by formula (2) is 0.055 or less in terms of weight ratio to the cycloalkanone (1), a process for producing the same, a process for producing a composition containing alkyl acetate (5) by using the cycloalkanone composition, and an alkyl acetate composition obtained by the process wherein n is an integer of 1 or 2, R1 and R2 each represent H, a C1 to C8 alkyl group etc., and R3 represents a C1 to C3 alkyl group.
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Page/Page column 9
(2008/06/13)
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- Synthesis of cis-Hedione and methyl jasmonate via cascade Baylis-Hillman reaction and Claisen ortho ester rearrangement
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The exocyclically unsaturated conjugated keto esters 10, obtained via a Claisen ortho ester rearrangement of the allylic hydroxy ketones 9, were either directly hydrogenated or partially isomerized into the endocyclically unsaturated tetrasubstituted didehydrojasmonoid intermediates 14, prior to a more selective hydrogenation with Pd/C in cyclohexane to the disubstituted oxocyclopentaneacetates 15 (Scheme 2). The key intermediates 9 were obtained either by a four-step sequence, including acetal protection/deprotection from enone 1, in the specific case of hydroxy ketone 9a (Scheme 1), or more directly and generally by a Baylis-Hillman reaction from cyclopent-2-en-1-one (16) and the appropriate aldehydes 17 (Scheme 2). The judicious choice of these aldehydes opens versatile modifications for the stereoselective introduction of the partially cis- or epimerized trans-C(2) jasmonoid side chain, while the Baylis-Hillman reaction, catalyzed by chiral [1,1′-binaphthalene]-2, 2′-diols (BINOLs) 19 (Scheme 3), may be efficiently conducted in a one-pot cascade fashion including the ortho ester Claisen rearrangement.
- Chapuis, Christian,Buechi, George H.,Wueest, Hans
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p. 3069 - 3088
(2007/10/03)
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- Process for producing cycloalkanone derivatives
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The present invention provides a process for producing 2-(1-hydroxyalkyl)cycloalkanone and/or 2-(1-hydroxyaryl)cycloalkanone in high yield and selectivity, as well as a process using the same to produce a cycloalkanone derivative useful as a perfume material and a physiologically active substance. Disclosed is a process for producing compound (3), which includes subjecting a cycloalkanone, and aldehyde (2) containing carboxylic acid (1), to aldol condensation in the presence of water and a basic catalyst, wherein the molar amount (referred to hereinafter as A) of the basic catalyst added is not less than the molar amount (referred to hereinafter as B) of the carboxylic acid (1) contained in the aldehyde (2) and the difference between A and B, that is, (A - B) is 0.06 mol or less per mol of the aldehyde (2) , as well as a process for producing compounds (7) and (8) by using the compound (3) obtained by the above process.
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- Method for producing 2-(alkyl)cycloalkenone
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A method for producing 2-(alkyl)cycloalkenone and a method for producing alkyl(3-oxo-2-alkylcycloalkyl) acetate and 5-alkyl-5-alkanolide which are useful as flavoring materials and physiologically active substances using the same are provided. A method for producing Compound (2) including the steps of: dehydrating Compound (1) using an acid catalyst until the conversion ratio of dehydration reaction reaches 20 to 90% based on Compound (1), thereby obtaining a mixture containing Compound (1) and Compound (3); and isomerizing Compound (3) while dehydrating the remaining Compound (1), and a method for producing Compound (5) or (6) using obtained Compound (2).
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- Serine carbonates
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Serine carbonates of formula I are precursors for organoleptic compounds, masking agents and antimicrobial agents. Further they are alternative substrates for malodor producing enzymes. The symbols in formula I are defined in claim 1.
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- Compounds having protected hydroxy groups
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The present invention relates to compounds with protected hydroxy groups of formula (I) These compounds are precursors for organoleptic agents, such as fragrances, and masking agents and for antimicrobial agents. When activated, the compounds of formula (I) are cleaved and form one or more organoleptic and/or antimicrobial compounds.
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- Compounds having protected hydroxy groups
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The present invention relates to compounds with protected hydroxy groups of formula (I) These compounds are precursors for organoleptic agents, such as fragrances, and masking agents and for antimicrobial agents. When activated, the compounds of formula (I) are cleaved and form one or more organoleptic and/or antimicrobial compounds.
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- Precursors for fragrant ketones and fragrant aldehydes
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The present invention refers to fragrance precursors of formula I for a fragrant ketone of formula II and one or more fragrant aldehydes or ketones of formula III and IV, These fragrance precursors are useful in perfumery, especially in the fine and functional perfumery.
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- Beta-ketoester compounds
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The beta-ketoesters of formula I are useful as precursors for organoleptic compounds, especially for flavors, fragrances and masking agents and antimicrobial compounds.
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- Ketone precursors for organoleptic compounds
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The invention discloses ketones of formula I: wherein, Y is an optionally substituted alkyl, cycloalkyl, or cycloalkylalkyl, wherein each alkyl group is straight or branched and each alkyl and cycloalkyl group is saturated or unsaturated; R1is hydrogen or a C1-6alkyl group that is substituted, saturated or unsaturated, straight or branched; A is a chromophoric substituted aromatic ring or ring system; n is an integer; and with the proviso that formula I is not 2-ethoxy-1-phenyl-ethanone. These compositions are useful for the delivery of organoleptic compounds, especially of flavors, fragrances, masking agents and antimicrobial compounds.
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- Synthesis of (±)-methyl epijasmonate and (±)-methyl dihydroepijasmonate by diastereoselective protonation
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The synthesis of (±)-methyl epijasmonate (1) was carried out by Michael addition of lithium diallylcuprate to enone 3 and diastereoselective enolate protonation with the chelating proton source 2-(methyliminomethyl)phenol (4; 85% ds), followed by ozonolysis, oxidation, esterification, and Lindlar hydrogenation. During the ozonisation, epimerization to the thermodynamically more stable trans-isomer takes place to some extent, so that 1 was isolated with a cis:trans ratio of 72:28. The analogous transformation of enone 7 with lithium diallylcuprate and 2-(methyliminomethyl)phenol (4) furnished ketone 8 with 94% ds; this was then transformed into (±)-methyl dihydroepijasmonate (2) with a cis:trans ratio of 91:9. The olfactory properties of this product are superior to those available from commercial sources.
- Krause, Norbert,Ebert, Sophia
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p. 3837 - 3841
(2007/10/03)
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- Synthesis of 12-Oxophytodienoic Acid (12-OxoPDA) and the Compounds of its Enzymic Degradation Cascade in Plants, OPC-8:0, -6:0, -4:0 and -2:0 (epi-Jasmonic Acid), as their Methyl Esters
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The synthesis of 12-Oxophytodienoic acid, and the compounds of its enzymatic degradation sequence, OPC-8:0, -6:0, -4:0 and -2:0, important plant metabolites derived from linolenic acid, is reported.The syntheses use the known cyclopent-3-ene-1,2-diacetic acid as an early intermediate, and this is derived from the Cope rearrangement of 5-vinyltrinorborn-2-ene via bicyclonona-3,7-diene.Iodolactonisation and tributyltin hydride reduction provides the key intermediate (3-oxo-2-oxabicyclooctan-6-yl)acetic acid for the OPC series, whilstphenylselenolactonisation and elimination provides the necessary unsaturated lactone (7-oxo-8-oxabicyclooct-2-en-4-yl)acetic acid for 12-oxoPDA.Members of the OPC-series were made by chain extending the saturated oxabicyclooctane acid: that for the OPC-4:0 involved double Arndt-Eistert reaction, whilst the intermediates for OPC-6:0 and -8:0 were made by Kolbe anodic crossed coupling.The lactones were than converted via their lactols, Wittig reaction, esterfication and oxidation, into the compounds of the OPC ester series, including OPC-2:0 (methyl epi-jasmonate).The unsaturate lactone 8-(7-oxo-8-oxabicyclooct-2-en-4-yl)octanoic acid required for 12-oxoPDA synthesis could also be prepared by anodic synthesis either from (7-oxo-8-oxa-bicyclooct-2-en-4-yl)acetic acid, or from its 2-phenylseleno-2,3-dihydro precursor as elimination occurred concomitantly during the reaction.Since yields were low, the unsaturated acid lactone was converted into its lactol and the (Z)-pent-2-enyl side-chain was inserted first.After TBDMS blocking of the cyclopentene hydroxy group, the side-chain was elaborated to give5-(pent-2-enyl)cyclopent-2-enylacetaldehyde and chain extension carried out by a Grignard-demesylation procedure.Sequential desilylation and depyranylation, followed by oxidation of the diol, gave 12-oxoPDA, isolated as its methyl ester.
- Crombie, Leslie,Mistry, Kamlesh M.
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p. 1981 - 1991
(2007/10/02)
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- ELECTROREDUCTIVE INTRAMOLECULAR COUPLING OF γ- AND δ-CYANOKETONES
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Electroreduction of γ- and δ-cyanoketones in i-PrOH gave cyclized products α-hydroxyketones and their dehydroxylated ketones, and this reaction was applied to the synthesis of dihydrojasmone, methyl dihydrojasmonate, and Rosaprostol.
- Shono, Tatsuya,Kise, Naoki
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p. 1303 - 1306
(2007/10/02)
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- Keten Silyl Acetal Chemistry; Simple Synthesis of Methyl Jasmonate and Related Compounds by Utilising Keten Methyl Dimethyl-t-butylsilyl Acetal
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Conjugate addition of keten silyl acetals to α,β-unsaturated carbonyl compounds in acetonitrile gave a quantitative yield of the corresponding methyl (3-trialkylsiloxyalk-2-enyl)acetates; subsequent site-specific electrophilic substitution yielded the corresponding 2-substituted 3-(alkoxycarbonylmethyl)alkanones.These novel addition and sequential alkylation reactions could be applied to a simple synthesis of methyl jasmonate, methyl didehydrojasmonate, and methyl dihydrojasmonate.
- Kita, Yasuyuki,Segawa, Jun,Haruta, Jun-ichi,Yasuda, Hitoshi,Tamura, Yasumitsu
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p. 1099 - 1104
(2007/10/02)
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- PREPARATION OF FIVE- AND SIX- MEMBERED CYCLIC KETONES BY THE PALLADIUM-CATALYZED CYCLIZATION REACTION. APPLICATION TO METHYL DIHYDROJASMONATE SYNTHESIS
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Methyl 3-oxo-8-phenoxy-6-octenoate (1) was cyclized using Pd(OAc)2-PPh3 as a catalyst to give 2-carbomethoxy-3-vinylcyclopentanone (2) and 2-carbomethoxy-4-cycloheptenone (3).The former was the main product in acetonitrile. 2-Alkylated 3-oxo-8-phenoxy-6-octenoates were converted mainly to the five-membered ketones.Based on this cyclization method, methyl dihydrojasmonate (8) was prepared from methyl 2-pentyl-3-oxo-8-phenoxy-6-octenoate (5).Methyl 3-oxo-9-phenoxy-7-nonenoate (10) was subjected to the palladium-catalysed cyclization to afford 2-carbomethoxy-3-vinylcyclohexanone (11) selectively without forming the eight membered ketone (12).
- Tsuji, Jiro,Kobayashi, Yuichi,Kataoka, Hideaki,Takahashi, Takashi
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p. 1475 - 1478
(2007/10/02)
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