- Scalable Aerobic Oxidation of Alcohols Using Catalytic DDQ/HNO3
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A selective, practical, and scalable aerobic oxidation of alcohols is described that uses catalytic amounts of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and HNO3, with molecular oxygen serving as the terminal oxidant. The method was successfully applied to the oxidation of a wide range of benzylic, propargylic, and allylic alcohols, including two natural products, namely, carveol and podophyllotoxin. The conditions are also applicable to the selective oxidative deprotection of p-methoxybenzyl ethers.
- Arseniyadis, Stellios,Clavier, Louis,Copin, Chloé,Fournier, Jean,Giffard, Jean-Fran?ois,Jean, Alexandre,Katsina, Tania,Macedo Portela Da Silva, Nayane,Tamion, Rodolphe
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supporting information
p. 856 - 860
(2020/07/14)
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- INSECTICIDAL COMPOSITION
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PROBLEM TO BE SOLVED: To provide a composition that can exhibit effective insecticidal action on insect pests. SOLUTION: An insecticidal composition comprises, e.g., a compound represented by general formula (1) in the figure. [R1 is a C1-10 alkyl group or the like, where the alkyl group and the like may be substituted with a halogen atom or the like; R2 is a hydrogen atom or the like, or R2 may bind a methoxy group binding a carbon atom adjacent to a carbon atom which R2 binds, to form a -O-CH2-O- group.] SELECTED DRAWING: None COPYRIGHT: (C)2021,JPO&INPIT
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Paragraph 0059-0061
(2020/10/27)
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- Methoxymethylation and benzyloxymethylation of aryl bromides
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The methoxymethylation and benzyloxymethylation of aryl bromides methodology was reported here. The transition metal free, high yielding one pot procedure will be useful for synthetic community.
- Panda, Biswajit
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p. 981 - 985
(2020/06/26)
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- Auto-Tandem Catalysis with Frustrated Lewis Pairs for Reductive Etherification of Aldehydes and Ketones
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Herein we report that a single frustrated Lewis pair (FLP) catalyst can promote the reductive etherification of aldehydes and ketones. The reaction does not require an exogenous acid catalyst, but the combined action of FLP on H2, R-OH or H2O generates the required Br?nsted acid in a reversible, “turn on” manner. The method is not only a complementary metal-free reductive etherification, but also a niche procedure for ethers that would be either synthetically inconvenient or even intractable to access by alternative synthetic protocols.
- Bakos, Mária,Gy?m?re, ádám,Domján, Attila,Soós, Tibor
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supporting information
p. 5217 - 5221
(2017/04/27)
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- INSECTICIDAL COMPOSITION
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PROBLEM TO BE SOLVED: To provide a composition that can exhibit effective insecticidal action on pests. SOLUTION: An insecticidal composition comprises a compound represented by general formula (1) [R1 is a C1-10 alkyl group or the like, where the alkyl group and the like may be substituted with a halogen atom and the like; R2 is a hydrogen atom and the like, or R2 may bind a methoxy group binding a carbon atom adjacent to a carbon atom which R2 binds, to form a -O-CH2-O- group]. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0059; 0060
(2017/09/29)
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- A gold catalytic the method for synthesizing calls the ether
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The invention provides a synthetic method of asymmetrical ether in the field of organic synthesis. The general equation of reaction is defined in the specification. In the equation, R-OH is benzyl alcohol, p-methoxy benzyl alcohol, tert-butyl alcohol, diphenyl carbinol or triphenylmethanol; and R'OH is common alkyl alcohol or a compound containing hydroxyl groups. A gold catalyst required by the reaction is Ph3PAuCl, Ph3PAuNTf2, HAuCl4, NaAuCl4, Ph3PAuOTf, Ph3PAuSbF6, IPrAuCl or nano-gold. A medium required by the reaction is solvent-free, and is toluene, mesitylene, 1,2-dichloroethane, tetrahydrofuran, acetonitrile or acetone. The reaction is implemented by heating through a microwave reactor. The method has advantages as follows: raw materials are easily available; operation is simple; the range of application is wide; atom economy is good; and the reaction is green.
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Paragraph 0042-0045; 0047-0049
(2017/02/28)
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- Photoredox Cross-Coupling: Ir/Ni Dual Catalysis for the Synthesis of Benzylic Ethers
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Single-electron transmetalation has emerged as an enabling paradigm for the cross-coupling of Csp3 hybridized organotrifluoroborates. Cross-coupling of α-alkoxymethyltrifluoroborates with aryl and heteroaryl bromides has been demonstrated by employing dual catalysis with a combination of an iridium photoredox catalyst and a Ni cross-coupling catalyst. The resulting method enables the alkoxymethylation of diverse (hetero)arenes under mild, room-temperature conditions. (Chemical Equation Presented).
- Karakaya, Idris,Primer, David N.,Molander, Gary A.
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supporting information
p. 3294 - 3297
(2015/07/15)
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- Organohalide-catalyzed dehydrative O-alkylation between alcohols: A facile etherification method for aliphatic ether synthesis
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Organohalides are found to be effective catalysts for dehydrative O-alkylation reactions between alcohols, providing selective, practical, green, and easily scalable homo- and cross-etherification methods for the preparation of useful symmetrical and unsymmetrical aliphatic ethers from the readily available alcohols. Mechanistic studies revealed that organohalides are regenerated as reactive intermediates and recycled to catalyze the reactions.
- Xu, Qing,Xie, Huamei,Chen, Pingliang,Yu, Lei,Chen, Jianhui,Hu, Xingen
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supporting information
p. 2774 - 2779
(2015/05/27)
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- Gold(I)-catalyzed synthesis of unsymmetrical ethers using alcohols as alkylating reagents
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A microwave-irradiated alcohol-protecting strategy based on gold catalysis utilizing benzyl alcohol, tert-butyl alcohol and triphenylmethanol as alkylating reagents has been developed. This protecting strategy has wide functional group tolerance with satisfactory yields for the majority of the selected alcohols. The mechanism of this transformation was probed with oxygen-18 isotope labelled alcohols assisted by GC-MS techniques and chemical kinetic experiments. This strategy provides an efficient, straightforward and alternative approach to the preparation of benzyl, tert-butyl and trityl ethers in organic synthesis.
- Liu, Yongxiang,Wang, Xiaoyu,Wang, Yanshi,Du, Chuan,Shi, Hui,Jin, Shengfei,Jiang, Chongguo,Xiao, Jianyong,Cheng, Maosheng
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p. 1029 - 1036
(2015/03/30)
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- Proton-exchanged montmorillonite-mediated reactions of methoxybenzyl esters and ethers
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Proton-exchanged montmorillonite (H-mont) was found to be an eco-friendly and cost-effective catalyst for the generation of O-methylated quinone methides (QM) from the corresponding p or o-methoxybenzyl esters and ethers. Nucleophilic trapping of the O-methylated QM with arenes, alcohols, 1,3-dicarbonyl compounds, silyl enol ethers, and allylsilanes has been carried out, respectively, leading to eco-friendly benzylation reactions. Using this protocol, H-mont-mediated deprotection of PMB-protected esters and ethers have been realized for the first time. This work would pave the way for further exploration in O-alkylated QM that are of chemical and biological significance.
- Chen, Dongyin,Xu, Chang,Deng, Jie,Jiang, Chunhuan,Wen, Xiaoan,Kong, Lingyi,Zhang, Ji,Sun, Hongbin
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p. 1975 - 1983
(2014/03/21)
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- PRO-FRAGRANCE COMPOUNDS
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A compound of Formula (I) wherein R1 represents a C3 to C20 hydrocarbon group derived from a fragrant alcohol of formula R1OH or from a fragrant aryl aldehyde or ketone of Formula (II), wherein: R2 is, independently, hydrogen atom, hydroxyl group, acetoxy group, -O(C=O)CH(CH3), optionally substituted C1-C6 alkyl group or C1-C6 alkoxy group, wherein any two of R2 may form an optionally substituted 5 or 6 membered ring, and R1 represents a radical derived from a fragrant alcohol of formula R1OH or from a fragrant aldehyde or from a fragrant aryl aldehyde or ketone of formula (II). The compounds are useful for example as a precursor for the prolonged delivery or release of fragrant compounds such as fragrant alcohols or aldehydes.
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Page/Page column 11; 16
(2014/12/09)
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- Selective catalytic synthesis of unsymmetrical ethers from the dehydrative etherification of two different alcohols
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The cationic ruthenium-hydride complex [(C6H6)(PCy3)(CO)RuH]+BF4- catalyzes selective etherification of two different alcohols to form unsymmetrically substituted ethers. The catalytic method exhibits a broad substrate scope while tolerating a range of heteroatom functional groups in forming unsymmetrical ethers, and it is successfully used to directly synthesize a number of highly functionalized chiral nonracemic ethers.
- Kim, Junghwa,Lee, Dong-Hwan,Kalutharage, Nishantha,Yi, Chae S.
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p. 3881 - 3885
(2015/01/16)
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- A very practical and selective method for PMB protection of alcohols
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A very simple, practical and efficient one-step heterogeneous protocol for the PMB protection of alcohols using Amberlyst-15 has been developed. The stability and hazard issues regarding PMBCl and PMBBr are totally avoided by directly using anisyl alcohol for the protection. Alcohols are protected in very good yields. The selective mono-PMB protection of diols as well as di-PMB protection of diols was achieved in good yields, along with the demonstration of recyclability of the catalyst.
- Chavan, Subhash P.,Harale, Kishor R.
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experimental part
p. 4683 - 4686
(2012/09/05)
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- Cross-coupling of mesylated phenol derivatives with potassium alkoxymethyltrifluoroborates
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Cross-coupling of mesylated phenol derivatives with various potassium alkoxymethyltrifluoroborates has been achieved. The corresponding aryl and heteroaryl alkoxymethyl compounds have been obtained with equal facility with both electron-rich and electron-poor substituents on the activated alcohol.
- Molander, Gary A.,Beaumard, Floriane
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supporting information; experimental part
p. 3948 - 3951
(2011/09/16)
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- Ferric perchlorate as an efficient and useful catalyst for the selective benzylation and methylation of alcohols with benzyl chloride and methyl iodide
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A mild and efficient method was developed for selective benzylation and methylation of hydroxyl compounds in the presence of a catalytic amount of ferric perchlorate. We showed that ferric perchlorate was very effective in selectively promoting the benzylation and methylation of primary aliphatic and benzylic alcohols versus secondary aliphatic alcohols and phenolic hydroxy groups. Graphical abstract: [Figure not available: see fulltext.]
- Behbahani, Farahnaz K.,Heravi, Majid M.,Oskooie, Hossien A.
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experimental part
p. 181 - 184
(2010/03/26)
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- One carbon homologation of halides to benzyl ethers
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The preparation of one carbon homologated benzyl ethers from alkyl and aromatic halides is reported. The coupling reaction is rapid and efficient at room temperature.
- Taber, Douglass F.,Paquette, Craig M.,Reddy, P. Ganapati
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supporting information; experimental part
p. 2462 - 2463
(2009/08/09)
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- Preparation of potassium alkoxymethyltrifluoroborates and their cross-coupling with aryl chlorides
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(Chemical Equation Presented) A wide variety of alkoxymethyltrifluoroborate substrates were prepared via SN2 displacement of potassium bromomethyltrifluoroborate with various alkoxides in excellent yields. These alkoxymethyltrifluoroborates were effectively cross-coupled with several aryl chlorides. This method provides a unique dissonant disconnect that allows greater flexibility in the design of new and improved synthetic pathways.
- Molander, Gary A.,Canturk, Belgin
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supporting information; experimental part
p. 2135 - 2138
(2009/05/26)
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- A highly efficient method for the reductive etherification of carbonyl compounds with triethylsilane and alkoxytrimethylsilane catalyzed by iron(III) chloride
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Facile reductive etherification of carbonyl compounds can be conveniently performed by reaction with triethylsilane and alkoxytrimethylsilane catalyzed by iron(III) chloride. The corresponding alkyl ethers, including benzyl and allyl ethers, of the reduced alcohols were obtained in good to excellent yields under mild reaction conditions.
- Iwanami, Katsuyuki,Seo, Hana,Tobita, Yuki,Oriyama, Takeshi
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p. 183 - 186
(2007/10/03)
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- Radical substitution with azide: TMSN3-PhI(OAc)2 as a substitute of in3
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TMSN3 and PhI(OAc)2 were found to promote high-yield azide substitution of ethers, aldehydes and benzal acetals. The reaction is fast and occurs at zero to ambient temperature in acetonitrile. However, it is essential for the reaction that TMSN3 is added subsequent to the mixture of PhI(OAc)2 and the substrate. A primary deuterium kinetic isotope effect was found for the azidonation of benzyl ethers both with TMSN3-PhI(OAc)2 and with IN3. Also a Hammett free energy relationship study of this reaction showed good correlation with σ+ constants giving with ρ-values of -0.47 for TMSN 3-PhI(OAc)2 and -0.39 for IN3. On this basis a radical mechanism of the reaction was proposed. The Rayal Society of Chemistry 2005.
- Pedersen, Christian Marcus,Marinescu, Lavinia Georgeta,Bols, Mikael
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p. 816 - 822
(2007/10/03)
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- N-nitroso-N,O-dialkylhydroxylamines: Preparation, structure, and mechanism of the hydronium ion catalysed solvolytic nitrous oxide extrusion reaction
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Eleven N-nitroso-N,O-dialkylhydroxylamines, RN(NO)OR′, have been prepared and the mechanisms of their hydronium ion catalysed solvolyses in aqueous solution which liberate nitrous oxide have been investigated. All reactions are first-order in substrate and first-order in hydronium ion, and the second-order rate constants at 25°C vary over a range of less than 140 in spite of considerable variation in substrate structure (R ranges from methyl to 4-methoxybenzyl to 2-adamantyl, for example) and changes in solvent composition (water with up to 50% methanol or 66% acetonitrile). Enthalpies and entropies of activation are qualitatively similar throughout the range (ΔH?= 72-93 kJ mol-1 and ΔS? = -19 to -57 J K-1 mol-1) which, with the product analyses, are accommodated by a mechanism involving pre-equilibrium protonation of the substrates followed by rate-limiting dissociation to give RN2O+ and HOR′. The oxodiazonium ion intermediate, RN2O+, then dissociates further to give the carbenium ion intermediate, R+, or suffers direct nucleophilic displacement of N2O by solvent (the external nucleophile) or by R′OH (the internal nucleophile liberated in the initial fragmentation). The carbenium ion, R+ (if formed), suffers nucleophilic capture either by solvent or by R′OH. When acetonitrile is the co-solvent (rather than methanol) for the N-(2-adamantyl) substrate 3g, the product of the Ritter reaction, 2-acetamidoadamantane, is detected. These nitrous oxide liberating reactions are compared with the nitric oxide liberating reactions of related N-nitrosohydroxylamines, and the origin of the difference between them is identified. The N(1)-nitroso group in the N,O-dibenzyl compound 3c is shown by X-ray crystallography to be essentially coplanar with the C and O atoms also bonded to N(1).
- Bhat, J. Ishwara,Clegg, William,Maskill, Howard,Elsegood, Mark R.J.,Menneer, Iain D.,Miatt, Peter C.
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p. 1435 - 1446
(2007/10/03)
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- Lewis Acid-Catalyzed Deprotection of p-Methoxybenzyl Ether
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The p-methoxybenzyl protecting group was readily removed from alcohols and phenols using catalytic amounts of AlCl3 or SnCl2 · 2H2O in the presence of EtSH at room temperature. Under these mild conditions other protecting groups such as methyl and benzyl ethers, p-nitrobenzoyl esters, TBDPS ethers and isopropylidene acetal were unchanged.
- Bouzide, Abderrahim,Sauvé, Gilles
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p. 1153 - 1154
(2007/10/03)
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- Al-NiCl(2°)6H2O-THF: A new, mild and neutral system for selective reduction of organic functional groups
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A mild and neutral reducing system consisting of Al-NiCl(2°)6H2O-THF has been developed and reacted with a series of organic compounds containing different functional groups in order to evaluate its synthetic utility. It was observed that this system very efficiently reduces the α-enones to the saturated ketones, aromatic aldehydes and ketones to the corresponding alcohols, nitriles and nitroarenes to amines, acid anhydrides and acid chlorides to aldehydes, disulphides to thiols and epoxides to the corresponding alcohols. On the other hand isolated double bonds, carboxylic acids, esters, lactones, primary, benzyl and allyl halides, aliphatic aldehydes and ketones and aliphatic nitro compounds were found to remain inert to this system. Furthermore, the reducing properties of Al-NiCl(2°)6H2O in several other organic solvents were also studied.
- Sarmah,Barua
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p. 8587 - 8600
(2007/10/02)
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- Skeletal Rearrangements on Chemical Ionization of Dibenzyl Ether and Derivatives
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Protonated molecular ions of dibenzyl ether, formed by chemical ionization using hydrogen and isobutane as reagent gases, undergo skeletal rearrangements to lose water and formaldehyde, both in the ion source and the flight path.The rearrangements have been elucidated by deuterium labelling and chemical substitution.The water lost contains the reagent proton and an aromatic hydrogen atom, and the aromatic hydrogen atoms have been shown to be mobile prior to the reaction.It is proposed that the skeletal rearrangement for water loss is initiated by protonation on the other oxygen atom, followed by benzyl migration.The formaldehyde loss contains benzylic hydrogen atoms exclusively, and it is proposed that the skeletal rearrangement is preceded by hydrogen rearrangement of an oxygen protonated molecular ion to a ring protonated molecular ion.Daughter ion structures are supported by comparisons of their collision induced dissociation spectra with those of isomeric ions prepared by alternative routes.
- Kingston, Eric E.,Shannon, James S.,Diakiw, Vladimir,Lacey, Michael J.
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p. 428 - 440
(2007/10/02)
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- Mechanism of Anodic Cleavage of Benzyl Ethers
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Kinetic isotope effects and substituent effects are utilized to elucidate the mechanism of the anodic oxidation of benzyl ethers at platinum in acetonitrile.All of the data, including some previously published results, are consistent with a mechanism involving phenylalkoxy carbonium ions.Much of the data is incompatible with a previous mechanistic proposal involving initial oxidative cleavage of the benzyl carbon-oxygen bond.
- Boyd, Jean W.,Schmalzl, Paul W.,Miller, Larry L.
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p. 3856 - 3862
(2007/10/02)
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