- Dibutyltin oxide mediated diastereoselective cyclodehydration/sulfonylation of 1,2,4-triols
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Dibutyltin oxide (Bu2SnO) mediated cyclodehydration or sulfonylation of 1,2,4-triols is predictably diastereoselective depending on the steric bulk of the substituents at C4. A larger difference (ΔA-value >1 kcal/mol) leads to the syn-1,2,4-triols favouring cyclodehydration (78-85%) to form 3-hydroxytetrahydrofurans, with the anti-1,2,4-triols favouring monosulfonylation (66-87%). Triols from symmetrical ketones preferentially undergo cyclodehydration in high yield (>75%) due to a gem-disubstituent effect. Thus, the 1,2,4-triols derived from simple cyclic ketones also favour cyclodehydration to form spirocyclic 3-hydroxytetrahydrofurans in 72-79% yields.
- Gamedze, Makhosazana P.,Nkambule, Comfort M.
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- Allylic Phosphates as Allyl Anion Synthons. Lithium-induced Allylation of Carbonyl Compounds
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Ultrasonication of allylic phosphates and carbonyl compounds with a lithium powder gave high yields of the corresponding homoallylic alcohols.
- Araki, Shuki,Butsugan, Yasuo
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- Scandium trifluoromethanesulfonate-catalyzed chemoselective allylation reactions of carbonyl compounds with tetraallylgermane in aqueous media
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Scandium(III) triflate-catalyzed allylation of carbonyl compounds with tetraallylgermane proceeded readily in aqueous nitromethane to afford homoallyl alcohols in excellent to good yields. The presence of H2O is indispensable for the allylation
- Akiyama, Takahiko,Iwai, Junko,Sugano, Megumi
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- GRIGNARD-TYPE ALLYLATION OF CARBONYL COMPOUNDS IN METHANOL BY THE ELECTROCHEMICALLY RECYCLED ALLYLTIN REAGENT.
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An electrochemical allylation of aldehydes and ketones in methanol was achieved by the electroreductive regeneration of diallyltin reagent in the presence of a catalytic amount of tin, affording the corresponding homoallyl alcohols in 72 - 91percent yield
- Uneyama, Kenji,Matsuda, Hiroyuki,Torii, Sigeru
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- Facile and Efficient Synthesis of Homoallylic Alcohols Using Allyl Bromide and Commercial Zinc Dust
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An efficient procedure for the preparation of homoallylic alcohols has been achieved by a simple reaction of an aldehyde or a ketone with allyl bromide and commercial zinc dust in tetrahydrofuran.
- Ranu, Brindaban C.,Majee, Adinath,Das, Asish R.
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- Protic solvent-promoted neutral allylation of aldehydes and ketones with 1,8-bis(allylstannyl)naphthalenes
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The allylation reactions of carbonyl compounds using 1,8-bis(dibutylstannyl)naphthalene 1 (R = Bu) were dramatically promoted by using a mixture of THF and CF3CH2OH (5 : 1) as solvent. The rate acceleration was due to the enhancement
- Asao, Naoki,Abe, Noriko,Tan, Zheng,Maruoka, Keiji
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- Indium-mediated allylation of carbonyl compounds in deep eutectic solvents
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This study describes, for the first time, the in situ generation of indium organometallic reagents in environmentally friendly deep eutectic solvents (DESs). The allylation process of different carbonyl compounds is achieved mediated by indium metal and u
- González-Gallardo, Nerea,Saavedra, Beatriz,Guillena, Gabriela,Ramón, Diego J.
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- Synthesis of homoallylic alcohols from ketones in water
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Homoallylic alcohols have been prepared in good yields by allylation of ketones with allyl bromide in the presence of stannous chloride dihydrate, zinc iodide, and ammonium chloride in water. Copyright Taylor & Francis LLC.
- Wang, Jun,Yuan, Gu
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- Solvent-Mediated Allylation of Carbonyl Compounds with Allylic Stannanes
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Methanol promotes the addition of allyltrimethylstannane (1a) to isobutyraldehyde (2a, 30 °C) yielding the corresponding homoallylic alcohol (3a), without the necessity for added catalyst. The corresponding reaction of aldehydes 2a-e or activated ketone 2
- Cokley, Teresa M.,Harvey, Peta J.,Marshall, Raymond L.,McCluskey, Adam,Young, David J.
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- Organometallic reactions in aqueous media: The allylations of carbonyl compounds mediated in Zn/CdSO4 and Zn/SnCl2 bimetal systems
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Zn/CdSO4 and Zn/SnCl2 bimetal systems were employed in the allylations of aldehydes or ketones in distilled water to afford the corresponding homoallylic alcohols in good yields. Also, the chemoselectivity was studied under the same
- Zhou, Cunliu,Zhou, Yuqing,Jiang, Jiaoyang,Xie, Zhen,Wang, Zhiyong,Zhang, Jiahai,Wu, Jihui,Yin, Hao
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- Indium-catalyzed allylation of carbonyl compounds with the Mn/TMSCl system
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Allylation of aldehydes and ketones with allyl bromide was performed with a catalytic amount of indium powder (from 0.01 to 0.1 equiv.) in THF in the presence of manganese and trimethylsilyl chloride as the reducing and oxophilic agent, respectively.
- Auge, Jacques,Lubin-Germain, Nadege,Thiaw-Woaye, Aurelie
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- Double coordination ability of bis(dimethylaluminum) sulfate toward carbonyl substrates
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New insight into the crucial role of bis(dimethylaluminum) sulfate as bidentate Lewis acid has been demonstrated using typical carbonyl allylation and Diels-Alder reaction in comparison with monodentate counterparts. The double coordination phenomenon of
- Hanawa, Hideo,Maekawara, Naomi,Maruoka, Keiji
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- Reactivity of hypervalent species of silicon: cleavage of the allyl-silicon bond
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The reactivities of the silicon-allyl bonds in two kinds of pentacoordinated silicon species CH2=CHCH2Si(o-O2C6H4)2-NMe4+ (1) and CH2=CHCH2Si(OCH2CH2)3N (2) has been compared.In the allyl transfer to carbonyl compounds under nucleophilic conditions (NaOMe, KF or Bu4NF) and electrophilic conditions (TiCl4, AlCl3, BF3) these two species show quite different behaviour.Complex 1 is activated by nucleophiles, while for 2 transfer occurs under electrophilic conditions.These results indicate that the reactivity of these species is a function of their overall charge and geometry.
- Cerveau, Genevieve,Chuit, Claude,Corriu, Robert J. P.,Reye, Catherine
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- Barbier coupling in water: SnCl2-mediated and Co(acac) 2-catalyzed allylation of carbonyls
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Co(acac)2·2H2O efficiently catalyzes SnCl 2-mediated Barbier coupling in water between carbonyls, including aromatic, aliphatic and α,β-unsaturated aldehydes, ketones, sugars and allyl bromide to afford the corresponding h
- Chaudhuri, Mihir K.,Dehury, Sanjay K.,Hussain, Sahid
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- General procedure for the synthesis of spirocyclic 3-hydroxy- and 3-oxotetrahydrofurans containing carbo- and heterocyclic fragments
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Reactions of cyclopentanone, cyclohexanone, N-substituted pyrrolidin-3-one and piperidin-4-one, and tetrahydropyran-4-one with allyl bromide in the presence of zinc and ammonium chloride gave the corresponding geminal hydroxy allyl derivatives. Treatment of the latter with sodium periodate in the presence of sodium metabisulfite resulted in their oxidative cyclization with formation of oxa spirocyclic alcohols containing carbo- and heterocyclic fragments. Swern oxidation of the spiro alcohols afforded the corresponding ketones which were characterized as 2,4-dinitrophenylhydrazones. Pleiades Publishing, Ltd., 2011.
- Moskalenko,Belopukhov,Ivlev,Boev
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- Metal-mediated Barbier-type carbonyl allylation under solvent-free conditions
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Zinc, tin, and indium mediated Barbier-type cross coupling between carbonyl compounds and allyl halides have been investigated without additional solvent. The indium mediated reactions proceed effectively under solvent free conditions. To a more limited e
- Yi, Xiang-Hui,Haberman, John X.,Li, Chao-Jun
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- Allylation of carbonyl compounds by allylic acetates using a cobalt halide as catalyst
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In acetonitrile as solvent and in the presence of a simple cobalt halide as catalyst, the reduction by zinc dust of a mixture of aldehydes or ketones and allylic acetates affords the corresponding homoallylic alcohols in good yields.
- Gomes, Paulo,Gosmini, Corinne,Perichon, Jacques
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- Scalable Continuous Synthesis of Organozinc Reagents and Their Immediate Subsequent Coupling Reactions
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The continuous synthesis of organozinc reagents and their immediately following subsequent also continuous consumption in catalyzed and noncatalyzed coupling reactions were investigated. In the first step, a bed of Zn turnings at variable liquid throughputs and concentrations of organic halide solutions was used, and the formed Zn organometallics were analyzed for quality control. They were then directly pumped into a second step, namely, Reformatsky, Saytzeff, and Negishi coupling reactions. In the organozinc halides' formation, a novel process window was employed by using a large molar excess of Zn turnings and investigating mechanical as well as chemical Zn activation. Subsequent couplings of the freshly prepared Zn organometallics were done using examples of a Reformatsky, Saytzeff, and Negishi coupling reaction. For the Zn organometallics' formation, a laboratory-scale reactor setup previously built for Grignard reagent formation was evaluated including a Zn replenishing unit; the same reactor was also used in the metal-catalyzed subsequent step (Negishi coupling). The main objective of this work was to establish the scalable continuous formation of Zn organometallic reagents enabling fast and safe process optimization, analyze the reagents for their purity, and then immediately consume them in various follow-up steps, always only leaving a very small amount of reactive and sensitive organometallic reagent in the setup. It was found that full conversion of the employed halides could be achieved within a single passage through the reactor with organozinc yields of 82-92%, as well as being able to successfully perform subsequent non- and metal-catalyzed coupling steps with yields of up to 92%. A pilot-scale setup allowing a liquid throughput of up to 3-5 L/h has also been built and is ready to be tested with the synthesis as established here.
- Menges-Flanagan, Gabriele,Deitmann, Eva,G?ssl, Lars,Hofmann, Christian,L?b, Patrick
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- A rapid and convenient synthesis of homoallylic alcohols by the barbier-grignard reaction
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The use of the Barbier-Grignard reaction, where premixed allyl bromide and the carbonyl compound are added to magnesium in ether, is reported for the synthesis of homoallylic alcohols. This reaction provides good to excellent yields of most homoallylic alcohols with minimal formation of Wurtz coupling products.
- Sormunen, Grant J.,Lewis, David E.
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- Facile Preparation of Spirolactones by an Alkoxycarbonyl Radical Cyclization–Cross-Coupling Cascade
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An alkoxycarbonyl radical cyclization–cross-coupling cascade has been developed that allows functionalized γ-butyrolactones to be prepared in one step from simple tertiary alcohol-derived homoallylic oxalate precursors. The reaction succeeds with aryl and vinyl electrophiles and is compatible with heterocyclic fragments in both coupling partners. This chemistry allows for the rapid construction of spirolactones, which are of interest in drug discovery endeavors.
- Weires, Nicholas A.,Slutskyy, Yuriy,Overman, Larry E.
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- Novel ultrasonication-assisted carbonyl allylation mediated by SnCl 2 in water
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Under ultrasonication, it was found that SnCl2 could efficiently mediate the aqueous Barbier reactions between carbonyl compounds and allyl bromide to give the corresponding homoallylic alcohols in high yields without using any Lewis acid catalyst.
- Wang, Jun,Yuan, Gu,Dong, Chang-Qing
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- Homoallylic Alcohols from Samarium Diiodide-mediated Coupling of Allylic Sulfones with Carbonyl Compounds
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Reduction of allylic sulfones with samarium diiodide gives allylsamarium species which react in situ with carbonyl compounds, yielding homoallylic alcohols.
- Clayden, Jonathan,Julia, Marc
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- Hydroalumination of terminal β-acetylene alcohols with lithium aluminum hydride
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Hydrogenation of terminal β-acetylene alcohols with lithium aluminum hydride in THF has afforded homoallylic alcohols. Decomposition of the intermediate organoaluminum complex with deuterated water, iodine, or pyridinium dibromide has evidenced about the non-regioselective hydride attack at the triple bond.
- Garibyan,Makaryan,Ogannisyan,Chobanyan
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- Masked allylic zinc reagents
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The preparation of allylic zinc reagents using the fragmentation of sterically hindered tertiary homoallylic alcohols is described.
- Jones, Philip,Millot, Nicolas,Knochel, Paul
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- A simple and inexpensive synthesis of 2-alkenals
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A simple and inexpensive method for the C2 homologation of aldehydes and ketone to 2-alkenals consists of the reaction with allylmagnesium bromide, O-acylation of the resultant 1-alken-4-ol, and ozonolysis.
- Chang,Uang,Wu,Yu
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- Carbonyl allylation of aldehydes and ketones with allylic chlorides catalyzed by immobilization of palladium in MCM-41
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The heterogeneous carbonyl allylation of aldehydes and ketones with allylic chlorides was achieved in DMF using SnCl2 as reducing agent at 25-40 °C in the presence of a 3-(2-aminoethylamino)propyl-functionalized MCM-41-immobilized palladium(II) complex [MCM-41-2N-Pd(II)], yielding a variety of homoallylic alcohols in good to high yields. This heterogeneous palladium catalyst exhibited higher activity than (N-propylethylenediamine)PdCl 2 and can be recovered and recycled by a simple filtration of the reaction solution and used for at least 5 consecutive trials without any decreases in activity.
- Zhao, Hong,Peng, Jian,Xiao, Ruian,Hao, Wenyan,Cai, Ming-Zhong
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- Allylic Sulfones as Allyl Anion Equivalents: Homoallylic Alcohols from Metal Catalysed Reactions of Sulfones with Aldehydes and Ketones
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Reduction of allylic sulfones with diethylzinc, catalysed by palladium(0), gives nucleophilic organometallic species, which react in situ with carbonyl compounds to give homoallylic alcohols in high yield.
- Clayden, Jonathan,Julia, Marc
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- A novel palladium-catalyzed coupling of epoxides with allyl bromide mediated by indium(I) chloride: A cascade epoxide rearrangement-carbonyl allylation
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A cascade epoxide rearrangement-aldehyde allylation was developed by using a combination of InCl and reusable heterogeneous mesoporous silica supported palladium catalysts.
- Jiang, Nan,Hu, Qingyuan,Reid, Carrolyn S.,Lu, Yunfeng,Li, Chao-Jun
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- Synthesis of homoallylic alcohols by allylation of aldehydes and ketones catalysed by a mesoporous material (mcm-41)-supported cyano palladium complex
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A variety of homoallylic alcohols has been conveniently synthesised in good to high yields by the allylation of aldehydes and ketones with allylic chlorides catalysed by an MCM-41-supported cyano palladium complex in DMF using SnCl2 as reducing agent. This polymeric palladium complex can be recovered and reused with some loss of activity.
- Yao, Fang,Huang, Bin,Cai, Mingzhong
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- AN EFFICIENT METHOD FOR THE PREPARATION OF HOMOALLYLIC ALCOHOL DERIVATIVES BY THE REACTION OF ALLYL IODIDE WITH CARBONYL COMPOUNDS IN THE PRESENCE OF STANNOUS HALIDE
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Allyl iodide reacts in situ under mild conditions with stannous halide to form allyltin dihaloiodide, which in turn reacts with carbonyl compounds in an aprotic solvent to give the corresponding homoallylic alcohol derivatives in good yields.
- Mukaiyama, Teruaki,Harada, Taira,Shoda, Shin-ichiro
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- Direct Transformation of Trialkyl Phosphates into Organolithium Compounds by a DTBB-Catalysed Lithiation
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The reaction of different alkylic or phenylic phosphates 1 with an excess of lithium powder and a catalytic amount of DTBB (5 mol percent) in the presence of an electrophile -Barbier-type reaction conditions- in THF at -30 deg C leads to the formation of the expected products 2, resulting from the reaction of the in situ generated organolithium compound with the corresponding electrophile.
- Guijarro, David,Mancheno, Balbino,Yus, Miguel
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- Allylation of aldehydes and ketones with allyl bromide and tin promoted by Me3SiCl and alcohol
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Allylation of aldehydes and ketones to give homoallylic alcohols can be carried out successfully with allyl bromide and metallic tin under anhydrous condition. The 64 ~ 89% yields of homoallyl alcohols are obtained by addition of chlorotrimethylsilane as a promoter in anhydrous methanol.
- Zhou,Yao,Chen,Wu
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- Allylation of Carbonyl Compounds Mediated by Germanium(II) Iodide
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Germanium(II) iodide reacts with allyl bromide in the presence of zinc iodide to afford allylgermanium(IV), which adds to carbonyl compounds to give the corresponding homoallylic alcohols in good yields.
- Hashimoto, Yukihiko,Kagoshima, Hirotaka,Saigo, Kazuhiko
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- Iron-catalyzed electrochemical allylation of carbonyl compounds by allylic acetates
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Homoallylic alcohols were synthesized from aldehydes or ketones and allylic acetates, using an electrochemical process catalyzed by iron complexes. We first studied the reactivity of allyl acetate, using N,N-dimethylformamide (DMF) or acetonitrile (AN) as solvent, FeBr2 as catalyst, and Fe as the sacrificial anode. Then we tested the regioreactivity of crotyl acetate and other allylic derivatives.
- Durandetti, Muriel,Meignein, Clotilde,Perichon, Jacques
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- Iridium-catalyzed carbonyl allylations by allylic alcohols with Tin(II) chloride
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Iridium complex [IrCl(cod)]2 can function as a catalyst for the allylation of aldehydes and ketones by allylic alcohols upon addition of an equimolar amount of SnCl2 in THF-H2O; the reaction is carried out between room temperature and 50 °C to give the corresponding homoallylic alcohols. Georg Thieme Verlag Stuttgart.
- Masuyama, Yoshiro,Chiyo, Toshiya,Kurusu, Yasuhiko
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- An efficient method for allylation of ketones with tetra-allylstannane
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A variety of ketones undergo an allylation reaction with tetra-allyltin in the presence of a catalytic amount of Cu(OTf)2 or Sn(OTf)2. The method was found to be superior to most of the known methods, which are efficient only with al
- Kamble, Rajesh M,Singh, Vinod K
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- Superacid Catalysis of the Addition of Allysilanes to Carbonyl Compounds
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The superacid TfOH2+B(OTf)4- (Tf = CF3SO2) was found to catalyse the addition of trialkylallysilanes to aldehydes and a ketone (the Sakurai reaction) at levels of ca. 0.5 molpercent; the reactions were clean, highly-yielding, and reg
- Davis, Anthony P.,Jaspars, Marcel
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- Remote Arylative Substitution of Alkenes Possessing an Acetoxy Group via β-Acetoxy Elimination
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Palladium-catalyzed remote arylative substitution was achieved for the reaction of arylboronic acids with alkenes possessing a distant acetoxy group to provide arylation products having an alkene moiety at the remote position. The use of β-acetoxy elimination as a key step in the catalytic cycle allowed for regioselective formation of unstabilized alkenes after chain walking. This reaction was applicable to various arylboronic acids as well as alkene substrates.
- Kakiuchi, Fumitoshi,Kochi, Takuya,Kumagai, Takaaki,Muto, Kazuma
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supporting information
p. 24500 - 24504
(2021/10/19)
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- A Mechanochemical Zinc-Mediated Barbier-Type Allylation Reaction under Ball-Milling Conditions
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A ball-milling-enabled zinc-mediated Barbier-type allylation reaction is reported. Notably, running the reaction in this manner renders it effective irrespective of the initial morphology of the zinc metal. The process is operationally simple, does not re
- Yin, JieXiang,Stark, Roderick T.,Fallis, Ian A.,Browne, Duncan L.
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p. 2347 - 2354
(2020/02/04)
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- Organocatalytic Trapping of Elusive Carbon Dioxide Based Heterocycles by a Kinetically Controlled Cascade Process
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A conceptually novel approach is described for the synthesis of six-membered cyclic carbonates derived from carbon dioxide. The approach utilizes homoallylic precursors that are converted into five-membered cyclic carbonates having a β-positioned alcohol group in one of the ring substituents. The activation of the pendent alcohol group through an N-heterocyclic base allows equilibration towards a thermodynamically disfavored six-membered carbonate analogue that can be trapped by an acylating agent. Various control experiments and computational analysis of this manifold are in line with a process that is primarily dictated by a kinetically controlled acylation step. This cascade process delivers an ample diversity of six-membered cyclic carbonates in excellent yields and chemoselectivities under mild reaction conditions.
- Bo, Carles,Kleij, Arjan W.,Limburg, Bart,Qiao, Chang,Sprachmann, Josefine,Villar-Yanez, Alba
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supporting information
p. 18446 - 18451
(2020/08/21)
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- Economical, Green, and Safe Route Towards Substituted Lactones by Anodic Generation of Oxycarbonyl Radicals
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A new electrochemical methodology has been developed for the generation of oxycarbonyl radicals under mild and green conditions from readily available hemioxalate salts. Mono- and multi-functionalised γ-butyrolactones were synthesised through exo-cyclisation of these oxycarbonyl radicals with an alkene, followed by the sp3–sp3 capture of the newly formed carbon-centred radical. The synthesis of functionalised valerolactone derivatives was also achieved, demonstrating the versatility of the newly developed methodology. This represents a viable synthetic route towards pharmaceutically important fragments and further demonstrates the practicality of electrosynthesis as a green and economical method to activate small organic molecules.
- Petti, Alessia,Leech, Matthew C.,Garcia, Anthony D.,Goodall, Iain C. A.,Dobbs, Adrian P.,Lam, Kevin
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supporting information
p. 16115 - 16118
(2019/11/05)
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- Merging metathesis and photochemical Csp3-H activation: Access to masked β-formyl hexanolides and their rearrangement to furofuranones
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β-Masked formyl hexanolides were prepared by a three-step sequence including esterification of homoallylic alcohols, ring-closing metathesis and the photochemically induced addition of dioxanyl radical. When treated under oxidative conditions, the adducts underwent cleavage of the ketal group leading after rearrangement to parent furofuranones, structures found in some biological active compounds.
- Glenadel, Quentin,Nassar, Youssef,Raffier, Ludovic,Veys, Sebastiaan,Piva, Olivier
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p. 5367 - 5373
(2018/07/06)
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- [bmim][Br] as an Inexpensive and Efficient Medium for the Barbier-Type Allylation Reaction Using a Catalytic Amount of Indium: Mechanistic Studies
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Barbier-type allylation reactions of aldehydes and ketones have been carried out with both unsubstituted and γ-substituted allyl bromides using only a catalytic amount (0.1 equiv.) of In metal in [bmim][Br], but not in H2O, organic solvents, or
- Dey, Papiya,Koli, Mrunesh,Goswami, Dibakar,Sharma, Anubha,Chattopadhyay, Subrata
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p. 1333 - 1341
(2018/04/02)
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- Preparation method and application of 2-hydroxymethyloxetane derivative
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The invention discloses a preparation method and application of a 2-hydroxymethyloxetane derivative. The method comprises the following steps that a compound II and a compound III are used as raw materials; Barbier reaction is performed to obtain a compound IV; olefinic bonds in the compound IV are cyclized and oxidized to obtain a compound V; under the alkaline condition, ring opening is performed to generate a compound VI; after ring closing reaction, a compound VII is obtained; finally, benzyl protecting groups are removed to obtain the 2-hydroxymethyloxetane derivative (the compound I).
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Paragraph 0085-0088
(2018/12/14)
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- CpTiCl2, an Improved Titanocene(III) Catalyst in Organic Synthesis
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Preparation, EPR analysis, and advantages in green organic chemistry of CpTiCl2, an improved single-electron transfer catalyst, are reported. Under mild conditions, this organometallic complex provides excellent yields of homoallylic and homopropargylic alcohols in Barbier-type allylation and propargylation reactions. Moreover, in the presence of a bidentate BOX ligand, Barbier-type cyclization reactions catalyzed by CpTiCl2 can be carried out in an enantioselective manner.
- Roldan-Molina, Esther,Padial, Natalia M.,Lezama, Luis,Oltra, J. Enrique
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supporting information
p. 5997 - 6001
(2018/11/23)
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- Green Organocatalytic Dihydroxylation of Alkenes
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An inexpensive, green, metal-free one-pot procedure for the dihydroxylation of alkenes is described. H2O2 and 2,2,2-trifluoroacetophenone were employed as the oxidant and organocatalyst, respectively, in this highly sustainable protocol in which a variety of homoallylic alcohols, aminoalkenes, and simple alkenes were converted into the corresponding polyalcohols in good to excellent yields. This process takes advantage of an epoxidation reaction followed by an acidic treatment in which water participates in the ring opening of the in situ prepared epoxide to lead to the desired product.
- Theodorou, Alexis,Triandafillidi, Ierasia,Kokotos, Christoforos G.
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p. 1502 - 1509
(2017/04/01)
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- Nucleo-Palladation-Triggering Alkene Functionalization: A Route to γ-Lactones
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An unprecedented strategy for the highly effective synthesis of γ-lactones from homoallylic alcohols was achieved by palladium catalysis in one step. The protocol affords aryl, alkyl, and spiro γ-lactones directly from readily available homoallylic alcohols in good yields with excellent functional group tolerance and high chemoselectivity under mild conditions.
- Zheng, Meifang,Chen, Pengquan,Huang, Liangbin,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 5756 - 5759
(2017/11/10)
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- Remarkable Influence of Cobalt Catalysis on Epoxide Ring-Opening with Sulfoxonium Ylides
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Cobalt demonstrates a remarkable ability to catalytically divert the course of epoxide to oxetane ring expansion via reaction with a sulfoxonium ylide. An expanded survey of transition-metal catalysts has confirmed that cobalt salts uniquely instead deliv
- Jamieson, Megan L.,Brant, Nicola Z.,Brimble, Margaret A.,Furkert, Daniel P.
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p. 3952 - 3956
(2017/08/29)
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- MeOH or H2O as efficient additive to switch the reactivity of allylSmBr towards carbonyl compounds
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A variety of carbonyl compounds were treated by allylSmBr (allylSmBr) with MeOH as the cosolvent to have further insights on the previously reported reductive coupling of aryl ketones mediated by Sm/alkyl halide/MeOH. The results demonstrate that the real reducing species in Sm/alkyl halide/MeOH system should be allylSmBr, and MeOH has elegantly switched the reactivity of allylSmBr from being nucleophilic to being good reductive coupling reagent. Besides, H2O was also found to be a useful additive to realize the pinacol coupling of aliphatic aldehydes and ketones promoted by allylSmBr.
- Li, Jianyong,Niu, Qingsheng,Li, Shanchan,Sun, Yuehao,Zhou, Qian,Lv, Xin,Wang, Xiaoxia
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supporting information
p. 1250 - 1253
(2017/03/10)
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- Synthesis of homoallylic amines and acylhydrazides by tin powder-promoted multicomponent one-pot allylation reactions
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An efficient process for the synthesis of homoallylic amines and N′-homoallylic hydrazides is developed from the one-pot reaction of carbonyl compounds, amines or N-acylhydrazines, allyllic bromide and tin powder using water as solvent. N-Acylhydrazines are found to be more reactive than amines in these processes. They can react not only with aldehydes but also with ketones to give the corresponding N′-homoallylic hydrazides. Copyright
- Ma, Junyan,Huang, Danfeng,Wang, Ke-Hu,Xu, Yanli,Chong, Siying,Su, Yingpeng,Fu, Ying,Hu, Yulai
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p. 571 - 576
(2016/07/16)
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- Mild bottom-up synthesis of indium(0) nanoparticles: Characterization and application in the allylation of carbonyl compounds
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Very reactive, monodisperse (4.0 ± 0.5 nm) spherical indium(0) nanoparticles have been generated in situ, in a simple, mild and efficient way, by fast reduction of commercially available indium(iii) chloride with lithium sand and a catalytic amount of 4,4′-di-tert-butylbiphenyl (DTBB) in THF, at room temperature, and in the absence of any anti-agglomeration additives or ligands. The as-synthesized bare InNPs were applied for the allylation of a variety of aldehydes and ketones. For most of the compounds tested, the corresponding homoallylic alcohols were obtained as the major product in good to excellent yield.
- Dorn, Viviana,Chopa, Alicia,Radivoy, Gabriel
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p. 23798 - 23803
(2016/03/12)
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- Novel pyrrolopyridine derivatives and its use as HIV inhibitor
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The present invention relates to a pyrrolopyridine derivative expressed as chemical formula 1, specifically a compound including a substituent group having an oxatane group in R1, its stereoisomer or racemic body, their pharmaceutically acceptable salts or their solvate, a manufacturing method thereof, and an antivirus composition containing the same as an active ingredient, wherein the compound expressed as chemical formula 1 has excellent selectivity and physiological activity with respect to wild type or resistant HIV-1 and therefore can be used as a remedy for AIDS.
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Paragraph 0132-0136; 0189; 0190; 0191; 0192; 0193
(2018/03/09)
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- A Green approach for allylations of aldehydes and ketones: Combining allylborate, mechanochemistry and lanthanide catalyst
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Secondary and tertiary alcohols synthesized via allylation of aldehydes and ketones are important compounds in bioactive natural products and industry, including pharmaceuticals. Development of a mechanochemical method using potassium allyltrifluoroborate salt and water, to successfully perform the allylation of aromatic and aliphatic carbonyl compounds is reported for the first time. By controlling the grinding parameters, the methodology can be selective, namely, very efficient for aldehydes and ineffective for ketones, but by employing lanthanide catalysts, the reactions with ketones can become practically quantitative. The catalyzed reactions can also be performed under mild aqueous stirring conditions. Considering the allylation agent and its by-products, aqueous media, energy efficiency and use of catalyst, the methodology meets most of the green chemistry principles.
- De Souza, Viviane P.,Oliveira, Cristiane K.,De Souza, Thiago M.,Menezes, Paulo H.,Alves, Severino,Longo, Ricardo L.,Malvestiti, Ivani
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- Efficient synthesis of homoallylic alcohols/amines from allyltributylstannane and carbonyl compounds/imines using iodine as catalyst under acetic acid-water medium
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This paper describes a general method for the synthesis of homoallylic alcohols and amines by nucleophilic addition reaction of allyltributylstannane to carbonyl compounds and aldimines where iodine acts as a catalyst in H2O/acetic acid (1:1) medium. Only 10 mol% of I2 is required for various organic transformations. By using this process, various homoallylic alcohols and amines are produced in good to excellent yields.
- Kalita, Pabitra Kumar,Borthakur, Susanta Kumar,Das, Runumi,Choudhury, Chandan Jyoti
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supporting information
p. 2444 - 2453
(2015/11/10)
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- Hydroxyl group-assisted palladium-catalyzed lactonization of homoallylic alcohols
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A convenient and highly efficient synthesis of α-methylene-γ- lactones through the palladium(II)-catalyzed lactonization of homoallylic alcohols with alkynamides has been reported. The hydroxyl group in the terminal olefins cooperates with the amide in alkynamides to promote the cyclization by suppressing the β-H elimination. This process provides a route to construct naturally occurring biologically multifunctional α-methylene-γ- lactones. The time has come to.i?lactonize: α-Methylene- γ-lactones are synthesized through the PdII-catalyzed lactonization of homoallylic alcohols with alkynamides. The hydroxyl group in the terminal olefins cooperates with the amide in alkynamides to promote the cyclization by suppressing the β-H elimination. This provides a route towards naturally occurring biologically multifunctional α-methylene- γ-lactones. Copyright
- Huang, Liangbin,Wang, Qian,Wu, Wanqing,Jiang, Huanfeng
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p. 561 - 566
(2014/03/21)
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- Nickel-catalyzed reductive allylation of ketones with allylic carbonates
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Nickel-catalyzed efficient umpolung allylation of ketones with allylic carbonates in the presence of zinc powder is developed, which accommodates a variety of allylic and ketone substrates. Although chiral ligand is necessary for the transformation, no enantioselectivity was observed. Georg Thieme Verlag Stuttgart New York.
- Zhao, Chenglong,Tan, Zhuozhen,Liang, Zhuye,Deng, Wei,Gong, Hegui
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supporting information
p. 1901 - 1907
(2014/07/22)
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- Cooperative titanocene and phosphine catalysis: Accelerated C-X activation for the generation of reactive organometallics
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The study presented herein describes a reductive transmetalation approach toward the generation of Grignard and organozinc reagents mediated by a titanocene catalyst. This method enables the metalation of functionalized substrates without loss of functional group compatibility. Allyl zinc reagents and allyl, vinyl, and alkyl Grignard reagents were generated in situ and used in the addition to carbonyl substrates to provide the corresponding carbinols in yields up to 99%. It was discovered that phosphine ligands effectively accelerate the reductive transmetalation event to enable the metalation of C-X bonds at temperatures as low as -40 °C. Performing the reactions in the presence of chiral diamines and amino alcohols led to the enantioselective allylation of aldehydes.
- Fleury, Lauren M.,Kosal, Andrew D.,Masters, James T.,Ashfeld, Brandon L.
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p. 253 - 269
(2013/03/14)
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- Rapid access to homoallylic alcohols via Pd(OAc)2 catalyzed Barbier type allylation in presence of DMAP
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DMAP was found to accelerate significantly the rate of Pd(OAc)2 catalyzed Barbier type allylation of carbonyl compounds by allylbromide using SnCl2·2H2O as reducing agent. Both aldehyde as well as ketones produced excellent yields within a short reaction time in the presence of 3 mol % of Pd(OAc)2 and 12 mol % of DMAP at room temperature. Aldehydes could be allylated within 5-10 min whereas, in case of ketones, the reaction completes in 45-120 min.
- Kashyap, Bishwapran,Phukan, Prodeep
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supporting information
p. 6324 - 6327
(2013/11/06)
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- SnCl2·2H2O-mediated Barbier-type allylation: A comparative evaluation of the catalytic performance of CuI and Pd(OAc) 2
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A systematic investigation has been carried out for the allylation of carbonyl compounds under SnCl2·2H2O-mediated Barbier-type conditions, using CuI and Pd(OAc)2 as catalysts. Ketones, which are not reactive under the influence of CuI, however, could be activated by using Pd(OAc)2 as a catalyst.
- Kalita, Pabitra Kumar,Phukan, Prodeep
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p. 1055 - 1062
(2013/11/06)
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- Catalytic use of zinc amide for transmetalation with allylboronates: General and efficient catalytic allylation of carbonyl compounds, imines, and hydrazones
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The efficient catalytic allylation of ketones, imines, and hydrazones with allylboronates using a catalytic amount of zinc amide is reported. In this reaction, the boron-to-zinc exchange process occurred smoothly to afford the corresponding allylzinc amides, and the desired allylation reactions proceeded in high efficiency (~0.1mol%). A mechanistic study revealed that transmetalation was a rate-determining step in the catalytic cycle, and also that the amide ligand on the zinc center played a key role in preparing reactive allylzinc species. Catalytic asymmetric allylations were also investigated, and high enantioselectivities were obtained using chiral diamine ligands. Copyright
- Cui, Yi,Li, Wei,Sato, Takehiro,Yamashita, Yasuhiro,Kobayashi, Shu
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supporting information
p. 1193 - 1205
(2013/06/04)
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- One-pot, solvent-free allylation or propargylation of carbonyl compounds mediated by the in situ generated Zn-Ag couple
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Zn-Ag couple which was in situ generated by zinc being oxidized with catalytic silver acetate was successfully applied to the one-pot and solvent-free allylation or propargylation of carbonyl compounds, in which high yields, regioselective addition, waste minimization and simple operation can be achieved.
- Yu, Changquan,Yang, Jian,Xia, Lingjie,Lu, Xiuyang
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experimental part
p. 2484 - 2486
(2012/08/27)
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- [Bmim] [Br] as a solvent and activator for the ga-mediated barbier allylation: Direct formation of an N -heterocyclic carbene from Ga metal
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The room-temperature ionic liquid (RTIL) [bmim][Br] has been found to be an excellent green and inexpensive medium for the Ga-mediated allylation of aromatic and aliphatic aldehydes and ketones. The RTIL activated the metal via formation of a Ga-N-heteroc
- Goswami, Dibakar,Chattopadhyay, Angshuman,Sharma, Anubha,Chattopadhyay, Subrata
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p. 11064 - 11070
(2013/02/22)
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- Stereoselective alkene isomerization over one position
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Although controlling both the position of the double bond and E:Z selectivity in alkene isomerization is difficult, 1 is a very efficient catalyst for selective mono-isomerization of a variety of multifunctional alkenes to afford >99.5% E-products. Many reactions are complete within 10 min at room temperature. Even sensitive enols and enamides susceptible to further reaction can be generated. Catalyst loadings in the 0.01-0.1 mol% range can be employed. E-to-Z isomerization of the product from diallyl ether was only -6 times as fast as its formation, showing the extremely high kinetic selectivity of 1.
- Larsen, Casey R.,Grotjahn, Douglas B.
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supporting information; experimental part
p. 10357 - 10360
(2012/08/08)
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- Study on the coupling of acyclic esters with alkenes - The synthesis of 2-(2-hydroxyalkyl)cyclopropanols via cascade cyclization using allylsamarium bromide
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The radical cyclization between aliphatic acyclic esters and alkenes was achieved unprecedentedly in the presence of allylsamarium bromide with HMPA and H2O as additives. The cascade radical cyclization-ring-opening- anionic cyclization allowed facile and efficient access to 2-(2-hydroxyalkyl) cyclopropanols from readily available materials.
- Tu, Yawei,Zhou, Liejin,Yin, Ruifeng,Lv, Xin,Flowers Ii, Robert A.,Choquette, Kimberly A.,Liu, Huili,Niu, Qingsheng,Wang, Xiaoxia
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supporting information
p. 11026 - 11028
(2013/01/15)
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- Concise synthesis of α-trisubstituted amines from ketones using n -methoxyamines
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Three-component allylation and cyanation utilizing a ketone and an N-methoxyamine are reported. The high nucleophilicity of the N-methoxyamine and high electrophilicity of the corresponding iminium ion enable the concise synthesis of α-trisubstituted amin
- Kurosaki, Yusuke,Shirokane, Kenji,Oishi, Takeshi,Sato, Takaaki,Chida, Noritaka
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supporting information; experimental part
p. 2098 - 2101
(2012/06/18)
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- Facile preparation of allylzinc species from allylboronates and zinc amide via a boron-to-zinc exchange process and their reactions with carbonyl compounds, imines and hydrazones
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Facile formation of allylzinc species from allylboronate and zinc amide was discovered. The boron-to-zinc exchange process occurred smoothly to afford the corresponding allylzinc amides, which were successfully employed in catalytic allylation reactions with electrophiles. Asymmetric catalysis using a chiral zinc amide is also reported.
- Cui, Yi,Yamashita, Yasuhiro,Kobayashi, Shu
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supporting information
p. 10319 - 10321
(2012/11/07)
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- Barbier allylation of aldehydes and ketones with aluminium and catalytic indium metal: An economical alternative
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An economical preparative protocol for the Barbier allylation of aldehydes and ketones in DMF, using aluminium foil in the presence of a catalytic amount of indium metal, is reported. All yields obtained are in general similar but slightly lower than those reported for the stoichiometric indium allylation. Aluminium alone failed to give rise to any detectable product. ARKAT-USA, Inc.
- Preite, Marcelo D.,Jorquera-Geroldi, Hugo A.,Perez-Carvajal, Andres
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experimental part
p. 380 - 388
(2011/06/09)
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- Mesoporous aluminosilicate-catalyzed allylation of carbonyl compounds and acetals
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A mesoporous aluminosilicate (Al-MCM-41) was found to be an effective heterogeneous catalyst for the reaction of both carbonyl compounds and acetals with allylsilanes to afford the corresponding homoallyl silyl ethers and homoallyl alkyl ethers, respectively. Both the mesoporous structure and the presence of aluminum moiety were indispensable for the high catalytic activity of Al-MCM-41. Moreover, Al-MCM-41 could catalyze the reaction of acetals chemoselectively in the presence of the corresponding carbonyl compounds. The solid acid catalyst Al-MCM-41 could be recovered easily by filtration and could be reused three times without a significant loss of catalytic activity.
- Ito, Suguru,Hayashi, Akira,Komai, Hirotomo,Yamaguchi, Hitoshi,Kubota, Yoshihiro,Asami, Masatoshi
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experimental part
p. 2081 - 2089
(2011/04/19)
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- Synthesis of tetrahydrofurans by cyclization of homoallylic alcohols with iodine/iodine(III)
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Tetrahydrofuran derivatives can be obtained by cyclofunctionalization of homoallylic alcohols bearing a terminal double bound by using [hydroxy(tosyloxy)iodo]benzene (HTIB, Kosers reagent) in the presence of a catalytic amount of I2 (20 mol %)
- Vasconcelos, Ramon S.,Silva Jr., Luiz F.,Giannis, Athanassios
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supporting information; experimental part
p. 1499 - 1502
(2011/05/06)
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- Aqueous electrosynthesis of carbonyl compounds and the corresponding homoallylic alcohols in a divided cell
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An aqueous paired electrosynthesis is studied in a divided cell. On graphite anode Br- was oxidized to Br2 and this generated Br2 oxidized alcohols to the corresponding carbonyl compounds while Sn2+ was reduced
- Zhang, Li,Zha, Zhenggen,Wang, Zhiyong,Fu, Shengquan
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scheme or table
p. 1426 - 1429
(2010/04/29)
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- An efficient electrochemical method for the paired synthesis of carbonyl compounds and homoallylic alcohols in a simple home-made cell
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An efficient electrochemical synthesis of carbonyl compounds and homoallylic alcohols was developed in excellent yields using a simple home-made cell. The catalytic redox behavior of the electrode surface and the reaction mechanism was investigated by cyc
- Zhang, Li,Zha, Zhenggen,Wang, Zhiyong
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supporting information; experimental part
p. 1915 - 1918
(2010/10/18)
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- Allyl transfer to aldehydes and ketones by Bronsted acid activation of allyl and crotyl 1,3,2-dioxazaborolidines
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Alkyl dioxazaborolidines are air-stable and often crystalline organoboranes. A variety of Bronsted acids activate allyl dioxazaborolidines to generate reactive allyl-transfer reagents in situ. These reagents add to aldehydes and ketones to generate the corresponding alcohols in good yields under mild conditions. The E- and Z-crotyl reagents react diastereoselectively with aldehydes and ketones to produce anti and syn adducts, respectively, a result consistent with a cyclic transition state (type I mechanism).
- Reilly, Maureen K.,Rychnovsky, Scott D.
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scheme or table
p. 4892 - 4895
(2010/12/25)
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- An electrochemical tandem reaction: One-pot synthesis of homoallylic alcohols from alcohols in aqueous media
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A tandem electrosynthesis of homoallylic alcohols from alcohols in one-pot was realized. In virtue of this one-pot electrosynthesis, the traditional reaction substrates of allylation were broadened from carbonyl compounds to alcohols.
- Zhang, Li,Zha, Zhenggen,Zhang, Zhenlei,Li, Yunfeng,Wang, Zhiyong
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supporting information; experimental part
p. 7196 - 7198
(2010/11/04)
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- Catalytic use of a soluble organoindium(III) species for allylation and crotylation of ketones with boronates
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The unprecedented use of a soluble organoindium species, indium(III) hexamethyldisilazide [In(III)(hmds)3], for catalytic carbon-carbon bond formations between ketones and boronates, is reported. Various functionalized tertiary homoallyl alcoho
- Yamaguchi, Miyuki,Morita, Naohide,Schneider, Uwe,Kobayashi, Shu
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experimental part
p. 1461 - 1465
(2010/08/20)
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- Mild and general zinc-alkoxide-catalyzed allylations of ketones with allyl pinacol boronates
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A general and efficient zinc-alkoxide-catalyzed allylation of a diverse array of ketones with allyl boronates is presented. The methodology is effective with 2 mol % of catalyst and with relatively short reaction times. Studies of the key exchange process are presented, which support a cyclic transition state for the boron to zinc exchange.
- Fandrick, Keith R.,Fandrick, Daniel R.,Gao, Joe J.,Reeves, Jonathan T.,Tan, Zhulin,Li, Wenjie,Song, Jinhua J.,Lu, Bruce,Yee, Nathan K.,Senanayake, Chris H.
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supporting information; experimental part
p. 3748 - 3751
(2010/11/18)
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- The solvent-free addition reaction of allylzinc bromide and carbony compounds
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The reactivity of organozincs could be enhanced dramatically under solvent-free conditions. Allylzinc bromide can react rapidly with aldehydes and ketones to give homoallylic alcohols in high yields in the absence of a catalyst under sol vent-free conditions in an open atmosphere at room temperature. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009.
- Zhang, Yumei,Jia, Xuefeng,Wang, Jin-Xian
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experimental part
p. 2983 - 2986
(2009/11/30)
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- Toluates: unexpectedly versatile reagents
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The mechanism of the monoelectronic reduction of aromatic esters has been investigated. The unexpected synthetic utility of the toluate moiety in the deoxygenation of alcohols and the allylation of ketones is also reported. Finally, the use of aromatic esters as robust, though easily removable, protecting groups is depicted.
- Lam, Kevin,Markó, István E.
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experimental part
p. 10930 - 10940
(2010/02/28)
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- Diallylation of 2,2-dialkylbenzodioxoles from TiCl4-mediated allylsilane reaction
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Reaction of aliphatic ketones with catechol afforded 2,2-dialkylbenzodioxoles. Treatment of these benzodioxoles with allyltrimethylsilane in the presence of titanium tetrachloride led to 4,4-dialkylhepta-1,6-dienes resulting from a diallylation process. R
- Galy, Nicolas,Moraleda, Delphine,Santelli, Maurice
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experimental part
p. 5238 - 5240
(2009/12/06)
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- Efficient solvent-free synthesis of homoallylic alcohols mediated by zinc-copper couple
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Under solvent-free conditions, it was found that zinc-copper couple could efficiently mediate the Barbier-type reaction of ketones and allyl bromide to give the corresponding homoallylic alcohols in high to excellent yields at room temperature. Georg Thieme Verlag Stuttgart.
- Zhou, Wenjun,Yan, Wenjun,Wang, Jin-Xian,Wang, Kehu
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p. 137 - 141
(2008/09/21)
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