1123-34-8Relevant articles and documents
Dibutyltin oxide mediated diastereoselective cyclodehydration/sulfonylation of 1,2,4-triols
Gamedze, Makhosazana P.,Nkambule, Comfort M.
, p. 1825 - 1829 (2015)
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.
Scandium trifluoromethanesulfonate-catalyzed chemoselective allylation reactions of carbonyl compounds with tetraallylgermane in aqueous media
Akiyama, Takahiko,Iwai, Junko,Sugano, Megumi
, p. 7499 - 7508 (1999)
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
Facile and Efficient Synthesis of Homoallylic Alcohols Using Allyl Bromide and Commercial Zinc Dust
Ranu, Brindaban C.,Majee, Adinath,Das, Asish R.
, p. 4885 - 4888 (1995)
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.
Indium-mediated allylation of carbonyl compounds in deep eutectic solvents
González-Gallardo, Nerea,Saavedra, Beatriz,Guillena, Gabriela,Ramón, Diego J.
, (2021)
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
Solvent-Mediated Allylation of Carbonyl Compounds with Allylic Stannanes
Cokley, Teresa M.,Harvey, Peta J.,Marshall, Raymond L.,McCluskey, Adam,Young, David J.
, p. 1961 - 1964 (1997)
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
Indium-catalyzed allylation of carbonyl compounds with the Mn/TMSCl system
Auge, Jacques,Lubin-Germain, Nadege,Thiaw-Woaye, Aurelie
, p. 9245 - 9247 (1999)
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.
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Okude,Y. et al.
, p. 3179 - 3181 (1977)
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Barbier coupling in water: SnCl2-mediated and Co(acac) 2-catalyzed allylation of carbonyls
Chaudhuri, Mihir K.,Dehury, Sanjay K.,Hussain, Sahid
, p. 6247 - 6251 (2005)
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
Metal-mediated Barbier-type carbonyl allylation under solvent-free conditions
Yi, Xiang-Hui,Haberman, John X.,Li, Chao-Jun
, p. 2999 - 3009 (1998)
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
Scalable Continuous Synthesis of Organozinc Reagents and Their Immediate Subsequent Coupling Reactions
Menges-Flanagan, Gabriele,Deitmann, Eva,G?ssl, Lars,Hofmann, Christian,L?b, Patrick
, p. 427 - 433 (2021)
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.
Facile Preparation of Spirolactones by an Alkoxycarbonyl Radical Cyclization–Cross-Coupling Cascade
Weires, Nicholas A.,Slutskyy, Yuriy,Overman, Larry E.
, p. 8561 - 8565 (2019)
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.
Novel ultrasonication-assisted carbonyl allylation mediated by SnCl 2 in water
Wang, Jun,Yuan, Gu,Dong, Chang-Qing
, p. 286 - 287 (2004)
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.
Hydroalumination of terminal β-acetylene alcohols with lithium aluminum hydride
Garibyan,Makaryan,Ogannisyan,Chobanyan
, p. 267 - 272 (2016)
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.
Reformatsky and Luche Reaction in the Absence of Solvent
Tanaka, Koichi,Kishigami, Satoshi,Toda, Fumio
, p. 4333 - 4334 (1991)
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Carbonyl allylation of aldehydes and ketones with allylic chlorides catalyzed by immobilization of palladium in MCM-41
Zhao, Hong,Peng, Jian,Xiao, Ruian,Hao, Wenyan,Cai, Ming-Zhong
, p. 2030 - 2034 (2011)
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.
Allylic Sulfones as Allyl Anion Equivalents: Homoallylic Alcohols from Metal Catalysed Reactions of Sulfones with Aldehydes and Ketones
Clayden, Jonathan,Julia, Marc
, p. 1905 - 1906 (1994)
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.
Synthesis of homoallylic alcohols by allylation of aldehydes and ketones catalysed by a mesoporous material (mcm-41)-supported cyano palladium complex
Yao, Fang,Huang, Bin,Cai, Mingzhong
, p. 366 - 369 (2009)
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.
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Ruppert,J.F.,White,J.D.
, p. 550 - 551 (1976)
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Allylation of aldehydes and ketones with allyl bromide and tin promoted by Me3SiCl and alcohol
Zhou,Yao,Chen,Wu
, p. 3081 - 3087 (1995)
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.
Iron-catalyzed electrochemical allylation of carbonyl compounds by allylic acetates
Durandetti, Muriel,Meignein, Clotilde,Perichon, Jacques
, p. 3121 - 3124 (2003)
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.
An efficient method for allylation of ketones with tetra-allylstannane
Kamble, Rajesh M,Singh, Vinod K
, p. 7525 - 7526 (2001)
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
Remote Arylative Substitution of Alkenes Possessing an Acetoxy Group via β-Acetoxy Elimination
Kakiuchi, Fumitoshi,Kochi, Takuya,Kumagai, Takaaki,Muto, Kazuma
supporting information, p. 24500 - 24504 (2021/10/19)
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.
Organocatalytic Trapping of Elusive Carbon Dioxide Based Heterocycles by a Kinetically Controlled Cascade Process
Bo, Carles,Kleij, Arjan W.,Limburg, Bart,Qiao, Chang,Sprachmann, Josefine,Villar-Yanez, Alba
supporting information, p. 18446 - 18451 (2020/08/21)
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.
