- Palladium-catalyzed anti-Markovnikov oxidative acetalization of activated olefins with iron(iii) sulphate as the reoxidant
-
This paper discloses the efficient palladium-catalyzed anti-Markovnikov oxidative acetalization of activated terminal olefins with iron(iii) sulfate as the reoxidant. This methodology requires mild reaction conditions and shows high regioselectivity toward anti-Markovnikov products and compatibility with a wide range of functional groups. Iron(iii) sulphate was the sole reoxidant used in this method. Various olefins like vinylarenes, aryl-allylethers, aryl or benzyl acrylates and homoallylic alcohols all reacted well providing anti-Markovnikov acetals, some of which represent orthogonally functionalized 1,3- and 1,4-dioxygenated compounds.
- Fernandes, Rodney A.,Kumar, Praveen,Yadav, Sandhya S.
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p. 427 - 443
(2022/01/20)
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- Photoredox Allylation Reactions Mediated by Bismuth in Aqueous Conditions
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Organometallic allylic reagents are widely used in the construction of C?C bonds by Barbier-type reactions. In this communication, we have described a photoredox Barbier allylation of aldehydes mediated by bismuth, in absence of other metals as co-reductants. Mild reaction conditions, tolerance of oxygen, and use of aqueous solvent make this photoredox methodology attractive for green and sustainable synthesis of homoallylic alcohols.
- Potenti, Simone,Gualandi, Andrea,Puggioli, Alessio,Fermi, Andrea,Bergamini, Giacomo,Cozzi, Pier Giorgio
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supporting information
p. 1624 - 1627
(2021/02/05)
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- Cp2TiCl2-Catalyzed Photoredox Allylation of Aldehydes with Visible Light
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A Barbier-type Cp2TiCl2-mediated (10 mol %) photoredox allylation of aldehydes under irradiation with visible light (blue light-emitting diodes (LEDs), 450 nm) and in the presence of an organic dye (3DPAFIPN, 5 mol %) with allylbromides is described.
- Bergamini, Giacomo,Calogero, Francesco,Cozzi, Pier Giorgio,Fermi, Andrea,Gualandi, Andrea,Guazzi, Simone,Mazzarini, Martino
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p. 3857 - 3863
(2020/03/26)
-
- Catalytic Dynamic Kinetic Resolutions in Tandem to Construct Two-Axis Terphenyl Atropisomers
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The defined structure of molecules bearing multiple stereogenic axes is of increasing relevance to materials science, pharmaceuticals, and catalysis. However, catalytic enantioselective approaches to control multiple stereogenic axes remain synthetically challenging. We report the catalytic synthesis of two-axis terphenyl atropisomers, with complementary strategies to both chlorinated and brominated variants, formed with high diastereo-and enantioselectivity. The chemistry proceeds through a sequence of two distinct dynamic kinetic resolutions: first, an atroposelective ring opening of Bringmann-type lactones produces a product with one established axis of chirality, and second, a stereoselective arene halogenation delivers the product with the second axis of chirality established. In order to achieve these results, a class of Br?nsted basic guanidinylated peptides, which catalyze an efficient atroposelective chlorination, is reported for the first time. In addition, a complementary bromination is reported, which also establishes the second stereogenic axis. These bromo-terphenyls are accessible following the discovery that chiral anion phase transfer catalysis by C2-symmetric phosphoric acids allows catalyst control in the second stereochemistry-determining event. Accordingly, we established the fully catalyst-controlled stereodivergent synthesis of all possible chlorinated stereoisomers while also demonstrating diastereodivergence in the brominated variants, with significant levels of enantioselectivity in all cases.
- Beleh, Omar M.,Miller, Edward,Toste, F. Dean,Miller, Scott J.
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supporting information
p. 16461 - 16470
(2020/10/26)
-
- Allylation of aldehydes by dual photoredox and nickel catalysis
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Here we report the application of dual nickel/photoredox catalysis to the allylation of aliphatic, aromatic and heteroaromatic aldehydes by using commercially available reagents. The process utilizes the combination of a Ni(ii) complex, [Ru(bpy)3]2+ as a photoredox catalyst, and allylacetate under blue LED irradiation, and allows the synthesis of a large variety of homoallylic alcohols.
- Gualandi, Andrea,Rodeghiero, Giacomo,Faraone, Adriana,Patuzzo, Filippo,Marchini, Marianna,Calogero, Francesco,Perciaccante, Rossana,Jansen, Thomas Paul,Ceroni, Paola,Cozzi, Pier Giorgio
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supporting information
p. 6838 - 6841
(2019/06/18)
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- BICYCLIC KETONE COMPOUNDS AND METHODS OF USE THEREOF
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The invention provides novel compounds having the general formula (I): (I) wherein R1, the A ring and the B ring are as described herein, pharmaceutical compositions including the compounds, and methods of using the compounds.
- -
-
Page/Page column 179
(2019/02/02)
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- Active bismuth mediated allylation of carbonyls/N-tosyl aldimines and propargylation of aldehydes in water
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Abstract: Active bismuth is synthesized by the chemical reduction of bismuth trichloride using freshly prepared sodium stannite solution as the reducing agent at room temperature. The as-synthesized active bismuth is applied as a reagent for the synthesis of homoallyl alcohol/homopropargyl alcohol from allyl bromide/propargyl bromide and carbonyl compounds in water at 50°C. The homoallyl amines are also synthesized from N-tosyl aldimines and allyl bromide using active bismuth reagent in good yields. No assistance of organic co-solvent, co-reagent, phase transfer catalyst or inert atmosphere is required for this reaction. The waste bismuth material obtained after the completion of the organic reaction can be reduced to active bismuth by sodium stannite solution and successfully reused for mediating the allylation of aldehydes. Graphical Abstract:: Synopsis Active bismuth mediated allylation/crotylation of aldehydes is developed in water to get homoallyl alcohols. The method is also applied for the allylation of N-tosyl aldimines and propargylation of aldehydes in water to achieve the homoallyl amines and homopropargyl alcohols, respectively. The reactions do not require the assistance of organic co-solvent, co-reagent, phase transfer catalyst or inert atmosphere.[Figure not available: see fulltext.].
- Sawkmie, Micky Lanster,Paul, Dipankar,Khatua, Snehadrinarayan,Chatterjee, Paresh Nath
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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
-
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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- Bi-mediated allylation of aldehydes in [bmim][Br]: A mechanistic investigation
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The inexpensive room temperature ionic liquid (RTIL), [bmim][Br] has been found to be a superior medium for the Bi-mediated Barbier-type allylation of aldehydes compared to other conventional solvents. It plays the dual role of a solvent and a metal activ
- Koli, Mrunesh,Chatterjee, Sucheta,Chattopadhyay, Subrata,Goswami, Dibakar
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supporting information
p. 2198 - 2203
(2018/09/04)
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- Copper-Promoted 6- endo-trig Cyclization of β,γ-Unsaturated Hydrazones for the Synthesis of 1,6-Dihydropyridazines
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A novel and efficient strategy for the synthesis of 1,6-dihydropyridazines via copper-promoted 6-endo-trig cyclization of readily available β,γ-unsaturated hydrazones have been developed. A series of 1,6-dihydropyridazines have been synthesized by this method with good yields, high functional group tolerance, and remarkable regioselectivity under mild conditions. Importantly, the 1,6-dihydropyridazines can be efficiently converted to biologically important pyridazines in the presence of NaOH.
- Guo, Yong-Qiang,Zhao, Mi-Na,Ren, Zhi-Hui,Guan, Zheng-Hui
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supporting information
p. 3337 - 3340
(2018/06/11)
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- An organoantimony complex with intramolecular N?→?Sb coordination as effective and recyclable catalyst for the allylation of aldehydes with tetraallyltin
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An air-stable hypervalent organoantimony (III) triflate complex (PhN(CH2C6H4)2SbOSO2CF3) having intramolecular N?→?Sb coordination was synthesized and characterized by techniques such as s
- Tan, Nianyuan,Nie, Tong,Au, Chak-Tong,Lan, Donghui,Wu, Shuisheng,Yi, Bing
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supporting information
p. 2592 - 2595
(2017/06/13)
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- Copper-mediated oxysulfonylation of alkenyl oximes with sodium sulfinates: a facile synthesis of isoxazolines featuring a sulfone substituent
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A novel and efficient Cu(OAc)2-mediated oxysulfonylation of alkenyl oximes with sodium sulfonates was developed. The reactions are easy to conduct, occur under mild conditions, and form a broad range of sulfone-substituted isoxazolines in good yields.
- Wang, Li-Jing,Chen, Manman,Qi, Lin,Xu, Zhidong,Li, Wei
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supporting information
p. 2056 - 2059
(2017/02/15)
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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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- 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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- CuI catalyzed Barbier type allylation of aldehyde in presence of S1,S2-dipyridin-2-yl ferrocene-1,1′-dicarbothioate as ligand
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Ferrocene based ligand S1 ,S2-dipyridin-2-yl ferrocene-1,1′-dicarbothioate has been prepared from 1,1′-ferrocene-dicarboxylic acid. The ligand has been used successfully in the SnCl2.2H2O mediated Barbier type a
- Kashyap, Bishwapran,Phukan, Prodeep
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p. 662 - 670
(2015/05/27)
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- Iodine(III)-Mediated Oxy-fluorination of Alkenyl Oximes: An Easy Path to Monofluoromethyl-Substituted Isoxazolines
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A highly regioselective intramolecular oxy-fluorination of alkenyl oximes was achieved. This new transformation represents an efficient method for the preparation of monofluoromethyl-substituted isoxazolines. The synthetic application of the oxy-fluorinat
- Kong, Weidong,Guo, Quanping,Xu, Zhaoqing,Wang, Guoqiang,Jiang, Xianxing,Wang, Rui
-
supporting information
p. 3686 - 3689
(2015/08/18)
-
- Oxime-mediated facile access to 5-methylisoxazoles and applications in the synthesis of valdecoxib and oxacillin
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A palladium-catalyzed efficient synthesis of 5-methylisoxazoles via oxime-mediated functionalization of unactivated olefins is described. The reaction affords a variety of 5-methylisoxazoles in moderate to good yields. To further demonstrate the utility of the method, the rapid synthesis of valdecoxib and oxacillin is reported. (Chemical Equation Presented).
- Dong, Kui-Yong,Qin, Hai-Tao,Bao, Xing-Xing,Liu, Feng,Zhu, Chen
-
supporting information
p. 5266 - 5268
(2015/01/09)
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- Copper-catalyzed oxyazidation of unactivated alkenes: A facile synthesis of isoxazolines featuring an azido substituent
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A novel and efficient Cu(OAc)2-catalyzed oxyazidation of unactivated alkenes was developed. The reactions are easy to conduct, occur under mild conditions, and form azido-substituted isoxazolines in good yields.
- Zhu, Liping,Yu, Hongmei,Xu, Zhaoqing,Jiang, Xianxing,Lin, Li,Wang, Rui
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supporting information
p. 1562 - 1565
(2014/04/17)
-
- Synthesis and structure of organobismuth chlorides and triflates containing (C,E)-chelating ligands (E=O, S) and their catalytic application in the allylation of aldehydes with tetraallyltin
-
Four air-stable hypervalent organobismuth compounds with (C,O)- or (C,S)-chelating ligands, namely, R2BiCl (R=2-(MeECH 2)C6H4; E=O (3), S (4)), [2-(MeOCH 2)C6H4]2BiOTf
- Tan, Nianyuan,Chen, Yi,Zhou, Yongbo,Au, Chak-Tong,Yin, Shuang-Feng
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p. 1363 - 1369
(2013/12/04)
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- Synthesis of Z-alkenes from Rh(I)-catalyzed olefin isomerization of β,γ-unsaturated ketones
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Developing olefin isomerization reactions to reach kinetically controlled Z-alkenes is challenging because formation of trans-alkenes is thermodynamically favored under the traditional catalytic conditions using acids, bases, or transition metals as the catalysts. A new synthesis of Z-alkenes from Rh(I)-catalyzed olefin isomerization of β,γ-unsaturated ketones to α,β-unsaturated ketones was developed, providing an easy and efficient way to access various Z-enones.
- Zhuo, Lian-Gang,Yao, Zhong-Ke,Yu, Zhi-Xiang
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supporting information
p. 4634 - 4637
(2013/10/08)
-
- 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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- 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)
-
- Lewis acid-catalyzed oxidative allylation: A new approach for the synthesis of homoallylic alcohols and amines directly from alcohols
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A new approach for the synthesis of homoallylic alcohols and amines directly from alcohols via one-pot sequential oxidation-Barbier reaction and oxidation-condensation-Barbier reactions, respectively, is reported. The protocol involves the one-pot ferric chloride-catalyzed oxidation of alcohols to the corresponding aldehydes with chloramine-T followed by indium-mediated Barbier allylation with allyl bromide to afford homoallylic alcohols in 70-90% overall yields. The ferric chloride-catalyzed condensation of aldehydes and oxidation by-product p-toluenesulfonamide followed by indium-mediated Barbier-type allylation of the resulting aldimines with allyl bromide affords homoallylic amines in 60-80% overall yields in the same reaction vessel. The present work demonstrates a new one-pot approach toward homoallylic alcohol and amine synthesis directly from alcohols. Copyright
- Srivastava, Vishnu P.,Patel, Rajesh,Yadav, Lal Dhar S.
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p. 695 - 700
(2011/05/06)
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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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supporting information; experimental part
p. 2081 - 2089
(2011/04/19)
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- Indium-mediated synthesis of homoallyl alcohols in the aqueous phase
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The indium-mediated Barbier-type allylation reaction of aldehydes with allyl bromide, which gives corresponding homoallyl alcohols, was investigated. The reaction medium and the effects of substituents were discussed in detail. The results showed that var
- Du, Zhengyin,Li, Yanchun,Wang, Fen,Zhou, Wanwei,Wang, Jin-Xian
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experimental part
p. 1664 - 1671
(2011/06/20)
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- Mild and efficient barbier allylation reaction mediated by magnesium powder under solvent-free conditions
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A novel and highly efficient synthesis of homoallylic alcohols is achieved by the allylation of carbonyl compounds using magnesium powder as mediator under solvent-free conditions. A series of aldehydes and ketones are converted to the corresponding homoa
- Li, Shunxi,Wang, Jin-Xian,Wen, Xiaoliu,Ma, Xiaofang
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experimental part
p. 849 - 855
(2011/03/19)
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- Asymmetric hydrocyanation of α,β-unsaturated ketones into β-cyano ketones with the [Ru(phgly)2(binap)]/C6H 5OLi catalyst system
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Enantioselective conjugate addition of HCN to α,β-unsaturated ketones catalyzed by the combined system of [Ru{(S)-phgly}2{(S)- binap}] and C6H5OLi has afforded β-cyano ketones in high yield (see scheme). No detectable amount of the corresponding 1,2-adduct was produced and tert-C4H9OCH3 was the solvent of choice. The cyanation was conducted with a substrate-to-catalyst molar ratio in the range of 200:1-1000:1 at -20-0°C. Copyright
- Kurono, Nobuhito,Nii, Noriyuki,Sakaguchi, Yusuke,Uemura, Masato,Ohkuma, Takeshi
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supporting information; experimental part
p. 5541 - 5544
(2011/07/08)
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- Rhodium-catalyzed reductive allylation of conjugated aldehydes with allyl acetate
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Reductive allylation of aryl and alkenyl aldehydes with allyl acetate catalyzed by the ionic diamine carbonyl rhodium complex, [Rh(TMEDA)(CO) 2][RhCl2(CO)2], under a carbon monoxide atmosphere afforded the corresponding homoallylic alcohols in good isolated yields.
- Vasylyev, Maksym,Alper, Howard
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supporting information; experimental part
p. 2710 - 2713
(2010/07/17)
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- Mg(NTf2)2xH22: An efficient catalyst for the synthesis of homoallylic alcohols in water
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An efficient method has been developed for the allylation of aldehydes with allytributylstannane in the presence of a catalytic amount of Mg(NTf 2)2xH22 at room temperature in water to afford the corresponding homoallylic
- Wang, Hong-She,Zeng, Jun-E
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experimental part
p. 378 - 384
(2010/04/02)
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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)
-
- Allylation of carbonyl compounds mediated by Aluminum/Fluoride salts in water
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A novel mediator (Al/KF) has been developed and employed in the Barbier-type alkylations of various aldehydes and ketones with alkyl halide in water. The carbonyl compounds could be effectively converted into corresponding homoallylic alcohol in good yiel
- Yuan, Shizhen,Liu, Jin,Xu, Ling,Zhu, Shaofeng
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experimental part
p. 578 - 582
(2010/10/04)
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- Indium-mediated Barbier-type allylation reaction in PEG400 and PEG400/H2O
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A green method for the allylation of aldehydes with allyl bromide mediated by indium in polyethylene glycol 400 (PEG400) and PEG400/H2O is described. Aldehydes with different substituents afforded the corresponding homoallylic alcohols in good to excellen
- Du, Zhengyin,Wang, Fen,Zhou, Wanwei,Wang, Jin-Xian
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experimental part
p. 475 - 477
(2010/12/25)
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- Potassium dodecatungsto cobaltate trihydrate: A new heterogeneous catalyst for the synthesis of homoallylic alcohols and amines
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A simple and efficient procedure has been developed for one-pot synthesis of homoallylic alcohols and amines in good to excellent yields using a variety of aldehydes, amines, and allyltributylstannane in the presence of a catalytic amount of potassium dod
- Nagarapu, Lingaiah,Paturi, Gopal,Apuri, Satyender,Bantu, Rajashaker,Bhavanthula, Renuka
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experimental part
p. 355 - 365
(2009/04/07)
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- Mild and efficient allylation of aldehydes with allyltributylstannane promoted by MgI2·(OEt)n etherate
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Allylation of aldehydes with allyltributylstannane was promoted in the presence of MgI2·(OEt)n to give homoallylic alcohols. The iodide anion and a noncoordinating reaction medium (CH 2Cl2) are the key features
- Zhang, Xingxian
-
-
- Mild and efficient allylation of aldehydes by using copper fluorapatite as catalyst
-
A facile synthesis of homoallylic alcohols is achieved by the allylation of aldehydes with allylicmetal reagents or allyl halides using copper fluorapatite (CuFAP) as catalyst under mild reaction conditions. A variety of aldehydes were converted to the co
- Lakshmi Kantam,Venkanna,Shiva Kumar,Balasubrahmanyam,Venkateswarlu,Sreedhara
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experimental part
p. 1497 - 1502
(2009/06/28)
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- Palladacyclic and platinacyclic catalysts for the allylation of aldehydes
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A range of palladacyclic and platinacyclic catalysts have been tested for activity in the allylation of aldehydes with allyl tributyltin. The bulky, π-acidic palladacycle [{Pd(μ-Cl){κ2-P,C-P(OC6H2-2,4-tBu2
- Bedford, Robin B.,Pilarski, Lukasz T.
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p. 4216 - 4219
(2008/09/20)
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- Microwave-assisted catalytic allylation of aldehydes promoted by a mesoporous silica-supported BINOL ligand in solid media
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An efficient and operationally simple method for catalytic allylation has been developed and its application in the microwave-assisted catalytic allylation of aldehydes in solid media was investigated. The Royal Society of Chemistry.
- Liu, Guohua,Gao, Yan,Lu, Xiaoquan,Liu, Mouming,Zhang, Fang,Li, Hexing
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supporting information; experimental part
p. 3184 - 3186
(2009/02/04)
-
- A novel palladium-catalyzed hydroalkoxylation of alkenes with a migration of double bond
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A novel palladium-catalyzed addition of alcohols to olefins was developed, in which a migration of double bond was involved. By this new method, a variety of allylic ethers were prepared with moderate to high yields under mild conditions. The Royal Society of Chemistry.
- Tan, Jiajing,Zhang, Zuhui,Wang, Zhiyong
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experimental part
p. 1344 - 1348
(2008/10/09)
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- The employment of indium nanoparticles in Barbier-type reaction of allylic chloride in water
-
Indium nanoparticles have been employed in the reactions of various carbonyl compounds with allyl (crotyl) chloride in water, affording the corresponding alcohols with high yields. The crotylation gave exclusive γ-adducts with a dominant syn-isomer. Copyr
- Li, Jiaming,Zha, Zhenggen,Sun, Lilin,Zhang, Yan,Wang, Zhiyong
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p. 498 - 499
(2007/10/03)
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- Novel and efficient method for the allylation of carbonyl compounds and imines using triallylaluminum
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This is the first report of the use of triallylaluminum as a reagent for the allylation of carbonyl compounds and imines. The allylation of ketimines without additional metal catalyst is known so far only in the case of the Grignard reagent. Triallylaluminum is a useful alternative to provide the homoallylic amines in excellent yield upon addition to aldimines and ketimines. The significant reactivity of this reagent was confirmed by its reaction with a sterically rigid ketone such as adamantanone to provide 1-adamantyl-3-buten-1-ol in 98% yield. The chemoselectivity of triallyl-aluminum was demonstrated by using different ketoesters. It is noteworthy that triallylaluminum is prepared from allyl bromide and aluminum metal, and not from a Grignard reagent, and that the procedure is operationally simple, leading to good to excellent product yields.
- Shen, Kao-Hsien,Yao, Ching-Fa
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p. 3980 - 3983
(2007/10/03)
-
- Identification of potent type I MetAPs inhibitors by simple bioisosteric replacement. Part 2: SAR studies of 5-heteroalkyl substituted TCAT derivatives
-
Systematic SAR studies on the thiazole ring 5-substituent of TCAT derivatives revealed that the introduction of a β-alkoxy or an amino group enhanced the inhibitory activity significantly. The present compounds are representative of specific Co(II)-MetAP1 inhibitors. Before the physiologically relevant metal ions for MetAPs are established, these small molecular compounds could be used as tools for detailed biological studies.
- Cui, Yong-Mei,Huang, Qing-Qing,Xu, Jie,Chen, Ling-Ling,Li, Jing-Ya,Ye, Qi-Zhuang,Li, Jia,Nan, Fa-Jun
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p. 4130 - 4135
(2007/10/03)
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- A recyclable electrochemical allylation in water
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(Chemical Equation Presented) To develop environmentally benign processes for C-C bond formation, electrochemistry is applied in a tin-mediated allylation reaction in water. In this electrochemical process, the corresponding homoallylic alcohols are prepa
- Zha, Zhenggen,Hui, Ailing,Zhou, Yuqing,Miao, Qian,Wang, Zhiyong,Zhang, Hanchang
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p. 1903 - 1905
(2007/10/03)
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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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p. 6247 - 6251
(2007/10/03)
-
- Rapid and solvent-free synthesis of homoallyl or homopropargyl alcohols mediated by zinc powder
-
A rapid and efficient procedure for the solvent-free synthesis of homoallylic and homopropargyl alcohols has been achieved by zinc-mediated Barbier-type reaction of carbonyl compounds at room temperature. Georg Thieme Verlag Stuttgart.
- Wang, Jin-Xian,Jia, Xuefeng,Meng, Tuanjie,Xin, Li
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p. 2838 - 2844
(2007/10/03)
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- SnCl2-mediated carbonyl allylation in fully aqueous media
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Systematic studies were performed on SnCl2-mediated carbonyl allylation reaction between aldehydes and allyl halides in fully aqueous media. Totally three valuable reaction systems were discovered, which were SnCl 2/CuCl2, SnCl2/TiCl3, and SnCl 2/PdCl2. They all provided good to excellent yields in the allylation of aliphatic and aromatic aldehydes under very mild and convenient conditions. SnCl2, by itself, was also found to be effective for the allylation reaction when allyl bromide was employed. However, the SnCl 2-only reaction could only tolerate very small amount of water as the solvent. The SnCl2/CuCl2, SnCl2/TiCl 3, and SnCl2/PdCl2-mediated reactions exhibited good regioselectivity favoring the γ-adduct when cinnamyl halides were employed as the allylation reagent. The same reactions with cinnamyl halides also showed good diastereoselectivity favoring the anti-product. Mechanistic studies using proton NMR techniques suggested that the additive (i.e., CuCl 2, TiCl3, PdCl2) could accelerate the formation of allyltin intermediate, but this step was shown not to be the most important for the allylation. Thus we proposed that the Lewis acid catalysis effect exerted by the additive was the main reason for the observed reactivity enhancement.
- Tan, Xiang-Hui,Hou, Yong-Quan,Huang, Chao,Liu, Lei,Guo, Qing-Xiang
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p. 6129 - 6136
(2007/10/03)
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- SnCl2/PdCl2-mediated aldehyde allylation in fully aqueous media
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Catalyzed by PdCl2, SnCl2 can efficiently mediate the allylation of various aldehydes with allyl chloride or bromide, but not with allyl alcohol, in fully aqueous media. The yield of the reaction is very high (90-100%), and the reaction is operationally simple, environmental benign and easy to scale up.
- Tan, Xiang-Hui,Hou, Yong-Quan,Shen, Bo,Liu, Lei,Guo, Qing-Xiang
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p. 5525 - 5528
(2007/10/03)
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- Gal3 catalysed nucleophilic addition of allyltrimethylsilane to aldehydes
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In dichloromethane, the nucleophilic addition of allyltrimethylsilane to aldehydes to give the corresponding homoallyl alcohols in good to excellent yields was catalysed effectively by gallium triiodide which was generated in situ by the reaction of gallium metal and iodine.
- Sun, Peipei,Xian, Yufang,Xiao, Yaping
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p. 216 - 217
(2007/10/03)
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- Iron-mediated allylation of aryl aldehydes in aqueous media
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Iron metal was found to be able to mediate the allylation reaction of aryl aldehydes in aqueous media with sodium fluoride as the promoter. The possible implication of an allyliron intermediate was examined.
- Chan, Tak Chung,Lau, Chak Po,Chan, Tak Hang
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p. 4189 - 4191
(2007/10/03)
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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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p. 286 - 287
(2007/10/03)
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- Active metallic indium mediated carbon-carbon bond formation in aqueous media: Barbier-type allylation of aldehydes
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Mediated by active metallic indium generated in situ from Sm/InCl 3.4H2O bimetallic system, aldehydes and allylic bromide undergo efficient Barbier-type allylation reaction to afford homoallylic alcohols in high yields under mild con
- Wu, Hua-Yue,Ding, Jin-Chang,Liu, Miao-Chang,Gao, Jing
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p. 160 - 162
(2007/10/03)
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