- Synthesis of Benzyl Alkyl Ethers by Intermolecular Dehydration of Benzyl Alcohol with Aliphatic Alcohols under the Effect of Copper Containing Catalysts
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Synthesis of benzyl alkyl ethers was performed in high yields by intermolecular dehydration of benzyl and primary, secondary, tertiary alcohols under the effect of copper containing catalysts. The formation of benzyl alkyl ethers occurs with participation of benzyl cation.
- Bayguzina,Gimaletdinova,Khusnutdinov
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p. 1148 - 1155
(2018/10/24)
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- Synthesis of ethers from carbonyl compounds by reductive etherification catalyzed by iron(III) and silyl chloride
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A simple iron- and silyl chloride catalyzed method for the preparation of symmetrical and nonsymmetrical ethers is presented. Various aldehydes and ketones were reductively etherified by using triethylsilane as a reducing agent in the presence of 2 mol% of iron(III) oxo acetate and 8 mol% of chloro(trimethyl)silane. The reactions can be carried out at ambient temperatures and pressures with ethyl acetate as the solvent.
- Savela, Risto,Leino, Reko
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p. 1749 - 1760
(2015/06/16)
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- Tandem ring-closing metathesis/transfer hydrogenation: Practical chemoselective hydrogenation of alkenes
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An operationally simple chemoselective transfer hydrogenation of alkenes using ruthenium metathesis catalysts is presented. Of great practicality, the transfer hydrogenation reagents can be added directly to a metathesis reaction and effect hydrogenation of the product alkene in a single pot at ambient temperature without the need to seal the vessel to prevent hydrogen gas escape. The reduction is applicable to a range of alkenes and can be performed in the presence of aryl halides and benzyl groups, a notable weakness of Pd-catalyzed hydrogenations. Scope and mechanistic considerations are presented.
- Connolly, Timothy,Wang, Zhongyu,Walker, Michael A.,McDonald, Ivar M.,Peese, Kevin M.
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supporting information
p. 4444 - 4447
(2015/01/09)
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- Mild and efficient capture and functionalisation of CO2 using silver(i) oxide and application to 13C-labelled dialkyl carbonates
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A high yielding three-component reaction between β-iodo ethylamine derivatives, MeOH and gaseous CO2 at ambient temperatures and pressures is reported using silver(i) oxide. Unfunctionalised alkyl iodides were also found to be effective in this transformation and their optimisation is also described. To highlight the ease and control with which gaseous CO 2 can be captured and functionalised under mild conditions, the reaction was performed using 13C-enriched CO2 to afford specifically 13C-carbonyl-labelled dialkyl carbonates with exquisite control of the isotopic purity in good yields and without the need for specialised equipment.
- Tunbridge, Gemma A.,Baruchello, Riccardo,Caggiano, Lorenzo
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p. 4613 - 4621
(2013/05/08)
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- Direct room-temperature lactonisation of alcohols and ethers onto amides: An "amide strategy" for synthesis
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Last-minute deal: A direct lactonisation of ethers and alcohols onto amides that proceeds at room temperature under mild conditions is reported (see scheme). This allows the effective saving of up to two unproductive, sequential deprotection operations in synthetic sequences. Mechanistic studies are described, and a new "amide strategy" that exploits the dual robustness/late-stage selective activation properties of this functional group is outlined. Copyright
- Valerio, Viviana,Petkova, Desislava,Madelaine, Claire,Maulide, Nuno
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supporting information
p. 2606 - 2610
(2013/03/14)
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- Batch to flow deoxygenation using visible light photoredox catalysis
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Herein we report a one-pot deoxygenation protocol for primary and secondary alcohols developed via the combination of the Garegg-Samuelsson reaction, visible light-photoredox catalysis, and flow chemistry. This procedure is characterized by mild reaction conditions, easy-to-handle reactants and reagents, excellent functional group tolerance, and good yields.
- Nguyen, John D.,Reiss, Barbara,Dai, Chunhui,Stephenson, Corey R. J.
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p. 4352 - 4354
(2013/06/05)
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- A novel method for synthesis of benzyl alkyl ethers using Vanadium-based metal complex catalysts
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A novel method has been developed for the synthesis of benzyl alkyl ethers in 25-85% yields via the reaction of toluene with alcohols in a CCl4 medium catalyzed by Et3N-activated VO(acac)2.
- Khusnutdinov,Bayguzina,Gallyamova,Dzhemilev
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p. 261 - 266
(2012/10/29)
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- Oxidation of acyclic alkenes and allyl and benzyl ethers with DIB/t-BuOOH/Mg(OAc)2
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Oxidation of (11Z)-1′,2′-didehydrostemofoline with DIB/TBHP/Mg(OAc)2·4H2O resulted in oxidative cleavage of the C-11-C-12 double bond instead of the desired allylic oxidation of the 1-butenyl side chain. Stemofoline gave a similar result. The oxidation of more simple terminal alkenes was regioselective and gave vinyl ketones while allyl and benzyl ethers gave acrylate and benzoate esters, respectively. Allyl and benzyl ethers could be chemoselectively oxidized in the presence of a terminal alkene or benzyl group. Oxidation of an internal alkene was poorly regioselective, in contrast to the oxidation of 1-substituted cyclohexenes.
- Sastraruji, Thanapat,Pyne, Stephen G.,Ung, Alison T.
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body text
p. 598 - 602
(2012/01/05)
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- New method for the synthesis of benzyl alkyl ethers mediated by FeSO 4
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The synthesis of benzyl alkyl ethers from benzyl bromides and alcohols using FeSO4 as a recoverable and reusable mediator has been described without use of base and cosolvent under mild conditions.
- Joshi, Girdhar,Adimurthy, Subbarayappa
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experimental part
p. 720 - 728
(2011/03/22)
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- Boryltrihydroborate: Synthesis, structure, and reactivity as a reductant in ionic, organometallic, and radical reactions
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Reaction of lithium 1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2- diazaborol-2-ide with borane·THF provides the first boryl-substituted borohydride: lithium [1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2- diazaborol-2-yl]trihydroborate. The c
- Nozaki, Kyoko,Aramaki, Yoshitaka,Yamashita, Makoto,Ueng, Shau-Hua,Malacria, Max,Lacote, Emmanuel,Curran, Dennis P.
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supporting information; experimental part
p. 11449 - 11451
(2010/10/04)
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- Radical deoxygenation of xanthates and related functional groups with new minimalist N-heterocyclic carbene boranes
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Minimalist N-heterocyclic carbene boranes 1,3-dimethylimidazol-2- ylideneborane and 2,4-dimethyl-1,2,4-triazol-3-ylideneborane are readily available and have low molecular weights. They exhibit superior performance to first-generation NHC-boranes, providi
- Ueng, Shau-Hua,Fensterbank, Louis,Lacote, Emmanuel,Malacria, Max,Curran, Dennis P.
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supporting information; experimental part
p. 3002 - 3005
(2010/08/20)
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- Nickel-catalyzed cross-coupling of unactivated alkyl halides and tosylate carrying a functional group with alkyl and phenyl Grignard reagents
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By the use of catalytic amounts of a nickel salt and a 1,3-butadiene, primary and secondary alkyl Grignard reagents undergo cross-coupling with alkyl bromides, iodide, and tosylate carrying a functional group such as amide, ester, and ketone at 0 °C in THF. The present procedure provides a simple, convenient, and practical method for construction of carbon chains in the presence of various functional groups. PhMgBr also gave the corresponding coupling product in a moderate yield.
- Singh, Surya Prakash,Terao, Jun,Kambe, Nobuaki
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scheme or table
p. 5644 - 5646
(2011/02/25)
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- Ionic and organometallic reductions with N-Heterocyclic carbene boranes
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Surgical reduction: N-Heterocyclic carbene-borane complexes such as depicted are neutral, organic soluble analogues of borohydride anions with a weak hydridic character, compatible with organometallic catalysis. They are applicable for surgical reductions in complex, multifunctional molecules.
- Chu, Qianli,Brahmi, Malika Makhlouf,Solovyev, Andrey,Ueng, Shau-Hua,Curran, Dennis P.,Malacria, Max,Fensterbank, Louis,Lacote, Emmanuel
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supporting information; experimental part
p. 12937 - 12940
(2010/05/19)
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- N-heterocyclic carbene boryl radicals: A new class of boron-centered radical
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Reduction of xanthates by N-heterocyclic carbene boranes (NHC-boranes) has been suggested to occur by a radical chain mechanism involving heretofore unknown NHC-boryl radicals. In support of this suggestion, both the expected borane dithiocarbonate product and an unexpected borane xanthate product have now been isolated. These are the first NHC-boranes with boron-sulfur bonds, and their structures have been secured by spectroscopic and crystallographic means. The first rate constants for H-atom transfer from an NHC borane complex were determined by using the ring opening of a substituted cyclobutylcarbinyl radical as a clock reaction. The rate constant for reaction of the NHC-borane with a secondary alkyl radical at ambient temperature is 4 × 104 M-1 s-1, and the Arrhenius function displayed an entropic term (log A term) that was typical for a bimolecular reaction. The B-H bond dissociation energy of an NHC-borane complex has been estimated at 88 kcal/mol. The putative NHC-boryl radical in these transformations has been detected by EPR spectroscopy. Spectral analysis suggests that it is a π-radical, analogous to the benzyl radical.
- Ueng, Shau-Hua,Solovyev, Andrey,Yuan, Xinting,Geib, Steven J.,Fensterbank, Louis,Lacote, Emmanuel,Malacria, Max,Newcomb, Martin,Walton, John C.,Curran, Dennis P.
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supporting information; experimental part
p. 11256 - 11262
(2009/12/03)
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- Chlorine borrowing: An efficient method for an easier use of alcohols as alkylation agents
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Chlorine functionalised tin dioxide nanoparticles proved able to partially convert alcohols into the corresponding chlorides, which act as alkylation agents with an increased electrophilicity, as evidenced on ether formation and Friedel-Crafts reactions.
- Makowski, Philippe,Rothe, Regina,Thomas, Arne,Niederberger, Markus,Goettmann, Frederic
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scheme or table
p. 34 - 37
(2010/04/22)
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- [IrCl2Cp*(NHC)] complexes as highly versatile efficient catalysts for the cross-coupling of alcohols and amines
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A comparative study on the catalytic activity of a series of [IrCl 2Cp*(NHC)] complexes in several C-O and C-N coupling processes implying hydrogen-borrowing mechanisms has been performed. The compound [IrCl2Cp*(InBu)] (Cp* = pentamethyl cyclopentadiene; InBu = 1,3-di-n-butylimidazolylidene) showed to be highly effective in the cross-coupling reactions of amines and alcohols, providing high yields in the production of unsymmetrical ethers and N-alkylated amines. A remarkable feature is that the processes were carried out in the absence of base, phosphine, or any other external additive. A comparative study with other known catalysts, such as Shvo's catalyst, is also reported.
- Prades, Amparo,Corberan, Rosa,Poyatos, Macarena,Peris, Eduardo
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scheme or table
p. 11474 - 11479
(2009/12/03)
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- Oxidation of benzylic alcohols and ethers to carbonyl derivatives by nitric acid in dichloromethane
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Nitric acid in dichloromethane may be successfully employed for the oxidation of benzylic alcohols and ethers to the corresponding carbonyl compounds. The proposed method proved to be of general applicability, affording very good yields of aldehydes and ketones and showing interesting chemoselectivity in many instances, allowing competitive aromatic nitration to be avoided, as well as - in the case of aldehydes - any further oxidation to carboxylic acids. The reaction probably proceeds by a radical mechanism, the active species in the oxidation process being NO2. Competitive formation of nitro esters was observed in some cases, whereas poor results were obtained with allylic and non-benzylic substrates. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Strazzolini, Paolo,Runcio, Antonio
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p. 526 - 536
(2007/10/03)
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- Lewis acid-catalyzed reductive etherification of carbonyl compounds with alkoxyhydrosilanes
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The TMSI-catalyzed reaction of aldehydes and ketones with alkoxydimethylsilanes gave unsymmetrical ethers in good to high yields. This reductive etherification is superior to the conventional method using two kinds of silicon reagents in terms of atom eff
- Miura, Katsukiyo,Ootsuka, Kazunori,Suda, Shuntaro,Nishikori, Hisashi,Hosomi, Akira
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p. 313 - 315
(2007/10/03)
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- BiBr3, an efficient catalyst for the benzylation of alcohols: 2-Phenyl- 2-propyl, a new benzyl-type protecting group
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The benzylation of aliphatic alcohols with various benzylic alcohols has been achieved in the presence of BiBr3 under mild conditions. 2- Phenylpropan-2-ol proved to be the most efficient and can be considered as a novel protecting group. (C) 2000 Elsevier Science Ltd.
- Boyer, Bernard,Keramane, El-Mehdi,Roque, Jean-Pierre,Pavia, André A.
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p. 2891 - 2894
(2007/10/03)
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- Synthesis of benzyl/allyl alkyl ethers from corresponding magnesium alkoxides
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In the presence of iodine, alcohols react with magnesium to produce magnesium alkoxides which are then treated with benzyl chloride or allyl bromide to produce benzyl alkyl ethers or allyl alkyl ethers.
- Lin, Ji-Mao,Li, Hui-Hui,Zhou, Ai-Min
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p. 5159 - 5160
(2007/10/03)
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- Fluorodestannylation. A Powerful Technique to Liberate Anions of Oxygen, Sulfur, Selenium, and Carbon
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Fluoride ions smoothly destannylate organotin chalcogenides to liberate nucleophilic chalcogenide ions; hence the first nucleophilic oxide (O2-) and selenide (Se2-) transfer agents are reported where the tin atom serves as "group 16 (VIB) transfer agent".In the presence of crown ethers or ammonium salts, this process results in a new way to generate "naked" nucleophiles.Ethers and selenides are formed in good to excellent yield.In addition, a useful C-C bond-forming reaction has been developed by using alkyltins with aldehydes and acid chlorides in the presence of fluroide ion.Aspects concerning reactivity and mechanism are presented.Finally, the generality of the fluorodestannylation procedure and the differences with parallel silicon chemistry are detailed.
- Harpp, David N.,Gingras, Marc
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p. 7737 - 7745
(2007/10/02)
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- CONTROLLED OXIDATION OF BENZYL ETHERS ON IRRADIATED SEMICONDUCTOR POWDERS
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Irradiation of a suspension of powdered TiO2, a photoactive semiconductor, in oxygen saturated acetonitrile leads to mild selective oxidation of substrates containing a benzylic methylene by conversion of that carbon to a carbonyl group.The method is shown to be synthetically useful for the preparation of esters from ethers and ketones from hydrocarbons.A critical analysis of the products and of the possible intermediates results in a plausible mechanistic pathway for these photooxidations.
- Pincock, James A.,Pincock, Alexandra L.,Fox, Marye Anne
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p. 4107 - 4118
(2007/10/02)
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