- Palladium-catalyzed anti-Markovnikov oxidative acetalization of activated olefins with iron(iii) sulphate as the reoxidant
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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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- Organocatalytic Asymmetric Synthesis of Cyclic Acetals with Spirooxindole Skeleton
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An organocatalytic asymmetric synthesis of cyclic acetal with spirooxindole skeleton has been developed via a domino reaction between isatin and γ-hydroxy enones. Bifunctional squaramide catalyst with adamantyl motif was found to be the most effective for the cascade reaction. With 10 mol% of the catalyst, the desired products were obtained in 1.8:1 to 9:1 diastereo- and 86% to >99% enantioselectivities from a range of substituted isatins and γ-hydroxy enones. (Figure presented.).
- Shikari, Amit,Mandal, Koushik,Chopra, Deepak,Pan, Subhas Chandra
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supporting information
p. 58 - 63
(2021/11/09)
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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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- Catalytic Photoredox Allylation of Aldehydes Promoted by a Cobalt Complex
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The preparation of homoallylic alcohols by addition of organometallic allyl compounds to carbonyls is an important strategy in organic chemistry. Allylating organometallic cobalt species can be generated employing stoichiometric quantities of Zn acting as reductant. To avoid the employment of stoichiometric amount of Zn, we have developed an allylation reaction of aromatic and aliphatic aldehydes promoted by photoredox catalysis in the presence of a cobalt complex, and we present herein a full account of our research. In the presence of the abundant CoBr2 (10 mol %), 4,4′-di-tert-butyl-2,2′-dipyridyl (dtbbpy, 10 mol %), allyl acetate (3 equiv.), [Ir(dtbbpy)(ppy)2]PF6 (ppy=2-phenylpyridine, 2 mol %), and N,N-diisopropylethylamine (4 equiv.), an allylation of aldehydes is taking place, in moderate to good yields. Substrates scope, limitations, and photophysical investigations of this new process are reported. (Figure presented.).
- Gualandi, Andrea,Rodeghiero, Giacomo,Perciaccante, Rossana,Jansen, Thomas Paul,Moreno-Cabrerizo, Cristina,Foucher, Charles,Marchini, Marianna,Ceroni, Paola,Cozzi, Pier Giorgio
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supporting information
p. 1105 - 1111
(2021/01/04)
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- Copper-Impregnated Magnesium-Lanthanum Mixed Oxide: A Reusable Heterogeneous Catalyst for Allylation of Aldehydes and Ketones
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Copper-impregnated magnesium-lanthanum mixed oxide [Cu(II)/Mg?La] was used as catalyst in synthesis of homoallylic alcohols from aldehydes and ketones using allyltributylstannane as the allylating source. The present protocol provides a great application
- Laha, Soumi,Likhar, Pravin R.,Pogula, Jaya,Sreedhar, B.
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supporting information
(2020/02/11)
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- Nickel-Catalyzed Hydroarylation of in Situ Generated 1,3-Dienes with Arylboronic Acids Using a Secondary Homoallyl Carbonate as a Surrogate for the 1,3-Diene and Hydride Source
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The nickel-catalyzed hydroarylation of 1,3-dienes with arylboronic acids using a secondary homoallyl carbonate as a surrogate for the 1,3-diene and hydride source has been developed. The synthetic strategy allowed an efficient access to a wide array of hydroarylation products in high yields with high functional group compatibility without the use of an external hydride source. Mechanistic experiments indicated that the alkene-directed oxidative addition and subsequent β-hydride elimination would be a critical process in this transformation.
- Hamaguchi, Takashi,Kawatsura, Motoi,Takahashi, Yoshiyuki,Tsuji, Hiroaki
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supporting information
(2020/02/15)
-
- 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)
-
- 3,3′-Bithiophene-Based Chiral Bisphosphine Oxides as Organocatalysts in Silicon-Derived Lewis Acid Mediated Reactions
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This account summarizes the development of new biheteroaromatic chiral bisphosphine oxides. 3,3′-Bithiophene-based phosphine oxides (BITIOPOs) have been successfully used as organocatalysts to promote Lewis base catalyzed, Lewis acid mediated stereoselective transformations. These highly electron-rich compounds, in combination with trichorosilyl derivatives (allyltrichlorosilane and silicon tetrachloride), generate hypervalent silicon species that act as chiral Lewis acids in highly diastereo- and enantioselective organic reactions. Several relevant examples related to these applications are discussed in detail. 1 Introduction 2 The BITIOPO Family 3 Enantioselective Opening of Epoxides 4 Enantioselective Allylation of Aldehydes 5 Stereoselective Direct (Double) Aldol-Type Reaction with Ketones 6 Stereoselective Direct Aldol-Type Reaction with Ester Derivatives 7 Conclusions.
- Benaglia, Maurizio,Benincori, Tiziana,Raimondi, Laura Maria,Rossi, Sergio
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p. 535 - 546
(2020/03/27)
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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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- Chiral Bisdiphenylphosphine Dioxides Bearing a Bis(triazolyl) Backbone as Promising Lewis Bases for Asymmetric Organocatalysis
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Two chiral C2-symmetric diphenylphosphine dioxides bearing an original bis(triazolyl) backbone were prepared starting from inexpensive and readily available precursors. The key step involves the simultaneous formation of five bonds in one chemi
- Sevrain, Nicolas,Volle, Jean-Noel,Pirat, Jean-Luc,Ayad, Tahar,Virieux, David
-
supporting information
p. 2267 - 2272
(2018/06/04)
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- Axial-Chiral Biisoquinoline N, N′-Dioxides Bearing Polar Aromatic C-H Bonds as Catalysts in Sakurai-Hosomi-Denmark Allylation
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The design, synthesis, and evaluation of axial-chiral biisoquinolines bearing polar aromatic C-H bonds as Lewis base catalysts are reported. Lewis bases containing the 3,5-bis(trifluoromethyl)phenyl group were found to be significantly more enantioselecti
- Reep, Carlyn,Morgante, Pierpaolo,Peverati, Roberto,Takenaka, Norito
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supporting information
p. 5757 - 5761
(2018/09/29)
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- Catalytic Nucleophilic Allylation Driven by the Water-Gas Shift Reaction
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The ruthenium-catalyzed allylation of aldehydes with allylic pro-nucleophiles has been demonstrated to be an efficient means to form carbon-carbon bonds under mild conditions. The evolution of this reaction from the initial serendipitous discovery to its general synthetic scope is detailed, highlighting the roles of water, CO, and amine in the generation of a more complete catalytic cycle. The use of unsymmetrical allylic pro-nucleophiles was shown to give preferential product formation through the modulation of reaction conditions. Both (E)-cinnamyl acetate and vinyl oxirane were efficiently used to form the anti-branched products (up to >20:1 anti/syn) and E-linear products (up to >20:1 E/Z) in high selectivity with aromatic, α,β-unsaturated, and aliphatic aldehydes, respectively. Attempts to render the reaction enantioselective are highlighted and include enantioenrichment of up to 75:25 for benzaldehyde.
- Denmark, Scott E.,Matesich, Zachery D.,Nguyen, Son T.,Milicevic Sephton, Selena
-
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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
-
supporting information
p. 2056 - 2059
(2017/02/15)
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- Facile access to zinc and cadmium selones: Highly active catalysts for Barbier reactions in aqueous media
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The syntheses and structures of five mononuclear zinc and cadmium selone complexes along with a polynuclear cadmium selone 1D chain were described. The mononuclear homoleptic zinc selone complexes were the first examples of structurally characterized zinc
- Babu, Chatla Naga,Srinivas, Katam,Prabusankar, Ganesan
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p. 6456 - 6465
(2016/05/09)
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- INDAZOLONES AS MODULATORS OF TNF SIGNALING
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The disclosure provides compounds of Formula (I) pharmaceutically acceptable salts, pro-drugs, biologically active metabolites, stereoisomers and isomers thereof wherein the variable are defined herein. The compounds of the disclosure are useful for treating immunological and oncological conditions.
- -
-
Page/Page column 50
(2016/10/31)
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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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- A Mild, efficient protocol for the synthesis of homoallylic alcohols using potassium allyltrifluoroborate promoted by salicylic acid
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Background: In the current decade, organotrifluoroborates have attained remarkable development in Chemistry and Materials. This can be evidenced by the increasing number of articles, review articles and patents devoted to this subject. As a consequence, the number of citations derived from papers dealing with this subject has experienced an exponential growth in the last years. The aim of this paper to describe a methodology based on the use of potassium allyltrifluoroborate for the synthesis of homoallylic alcohols using water as a co-solvent and under mild reaction conditions. Methods: The methodology is very robust (wide range of aldehydes) and simple, it uses low catalyst loadings and it is synthetically useful because it could be applied for the synthesis of more complex compounds. In addition, detailed experimental procedures, including the preparation of the starting materials, as well as the corresponding 1H, 13C, 19F and 11B spectra for all synthesized compounds are provided. Results: The method is environmentally friendly while it uses water as a solvent and the desired compounds containing different functionalities were obtained in moderate to good yields (60-93%) without the need of further purification in a very chemo- and regioselective way. Conclusion: Salicylic acid can efficiently promote the allylation of aldehydes using potassium allyltrifluoroborate at room temperature to yield the corresponding homoallylic alcohols in moderate to good yields. The method is efficient and environmentally friendly while it uses water as co-solvent. In addition the method is regio- and chemoselective and could be applied in the synthesis of more complex homoallylic alcohols.
- Silva, Jadson F.,Lima, Josefa A.C.,De Freitas, Jucleiton J.R.,Freitas, Ladjane P.S.R.,Menezes, Paulo H.,Freitas, Juliano C.R.
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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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- Oxime-mediated oxychlorination and oxybromination of unactivated olefins
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An oxime-mediated oxychlorination and oxybromination of unactivated olefins relying on palladium catalysis has been developed. A wide range of chlorinated and brominated isoxazolines has been synthesized in moderate to good yields. To demonstrate the value of the method, the brominated isoxazoline has been further converted to other useful synthetic feedstock.
- Dong, Kui-Yong,Qin, Hai-Tao,Liu, Feng,Zhu, Chen
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supporting information
p. 1419 - 1422
(2015/03/04)
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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
-
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)
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- A chiral bipyridyl alcohol for catalytic enantioselective Nozaki-Hiyama-Kishi allylation of aldehydes and ketones
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A class of bipyridyl alcohol ligands has been developed. A catalyst synthesized using a chromium(II)-ligand promotes the enantioselective Nozaki-Hiyama-Kishi (NHK) allylation of aldehydes and ketones with allylic halides. The allylation of various aromati
- Chen, Rui-Yu,Dhondge, Attrimuni P.,Lee, Gene-Hsian,Chen, Chinpiao
-
supporting information
p. 961 - 966
(2015/03/30)
-
- A Ce(OTf)3/PyBox catalyzed enantioselective Hosomi-Sakurai reaction of aldehydes with allyltrimethylsilane
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An efficient enantioselective Hosomi-Sakurai reaction catalyzed by a chiral Ce(OTf)3/PyBox complex has been explored. In the presence of 20 mol% of a chiral catalytic complex prepared in situ from Ce(OTf)3 and 2,6-bis[(S)-4-isopropyl
- Zhao, Song,Zhang, Xulong,Zhang, Yuwei,Yang, Huanhuan,Huang, Yan,Zhang, Kui,Du, Ting
-
supporting information
p. 7734 - 7737
(2015/10/12)
-
- 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
-
supporting information
p. 1562 - 1565
(2014/04/17)
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- Copper-catalyzed 5-endo-trig cyclization of ketoxime carboxylates: A facile synthesis of 2-arylpyrroles
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A novel and facile copper-catalyzed 5-endo-trig cyclization of ketoxime carboxylates for the synthesis of 2-arylpyrroles has been developed. The reaction tolerates a range of functional groups and is a practical procedure for rapid synthesis of 2-arylpyrroles in high yields under mild conditions. the Partner Organisations 2014.
- Du, Wei,Zhao, Mi-Na,Ren, Zhi-Hui,Wang, Yao-Yu,Guan, Zheng-Hui
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supporting information
p. 7437 - 7439
(2014/07/07)
-
- Oxazoline derivatives tagged with tosylated amino acids as recyclable organocatalysts for enantioselective allylation of aldehydes
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A series of amino acid-based oxazoline compounds have been prepared and successfully applied to the enantioselective allylation reaction of aldehydes. The fine-tuning of the structure of the oxazolines led to (S,S)-4 as an efficient organocatalyst which gave homoallyl alcohols in good yield (up to 90%) and excellent ee (up to 99%) for a wide range of substrates including aromatic, hetero-aromatic and α,β-unsaturated aldehydes. The chiral organocatalyst was synthesized in three easy steps with an overall 88% yield and successfully recycled for up to three cycles. On the basis of the experimental observations and NMR studies, a probable mechanism was proposed for this reaction.
- Ghosh, Debashis,Sadhukhan, Arghya,Maity, Nabin Ch.,Abdi, Sayed H. R.,Khan, Noor-Ul H.,Kureshy, Rukhsana I.,Bajaj, Hari C.
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p. 12257 - 12265
(2014/03/21)
-
- Metal free synthesis of homoallylic alcohols promoted by ultrasound
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The use of ultrasound irradiation to promote the allylation of aldehydes containing different functionalities with potassium allyltrifluoroborates is described. The method features the use of a minimum amount of acetone as solvent, without any other catalyst or promoter. The products were obtained in high yields, short reaction times, at room temperature and without the need of further purification.
- Freitas, Jucleiton José R.,Couto, Túlio R.,Cavalcanti, Italo H.,Freitas, Juliano C.R.,Oliveira, Roberta A.,Menezes, Paulo H.
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p. 1609 - 1614
(2014/06/09)
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- A practical procedure of low valent tin mediated Barbier allylation of aldehydes in wet solvent
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Use of aluminium as the reducing metal in spontaneous bimetal redox reaction has been elegantly exploited for allylation/crotylation of aldehydes in wet solvent. Here, low valent tin was prepared in situ by reduction of SnCl2·2H2O wi
- Vilanova, Conxín,Sánchez-Péris, María,Roldán, Steven,Dhotare, Bhaskar,Carda, Miguel,Chattopadhyay, Angshuman
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p. 6562 - 6567
(2013/11/19)
-
- Diastereoselective oxidative α-amination of aliphatic aldehydes catalyzed by iodine: Synthesis of syn-γ-hydroxy-α-amino acetals
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Aldehydes can react with secondary amines to give α-amino acetals via the α-amination of aliphatic aldehydes catalyzed by iodine. The presence of an asymmetric hydroxylated center at the γ-position of the aldehyde was found to induce the stereoselective a
- Zhang, Yun-Xiao,Zhang, An-Qi,Tian, Jie-Sheng,Loh, Teck-Peng
-
supporting information
p. 8387 - 8394
(2013/12/04)
-
- Rapid access to homoallylic alcohols via Pd(OAc)2 catalyzed Barbier type allylation in presence of DMAP
-
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
-
supporting information
p. 6324 - 6327
(2013/11/06)
-
- 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)
-
- An efficient route for the allylation of arylaldehydes to give enantiopure homoallylic alcohols
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An efficient asymmetric synthesis of homoallylic alcohols is described by the allylation of carbonyl compounds using organocatalysts as chiral directors in the presence of tin metal. The effect of chiral environment is also studied on the allylation reactions. This method allows us to obtain two different enantiomers of homoallylic alcohol in the presence of the corresponding chiral compound. The protocol is applied to various aldehydes to obtain high yields and excellent enantioselectivities for the corresponding homoallylic alcohols.
- Thorat, Prashant B.,Goswami, Santosh V.,Bhusare, Sudhakar R.
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p. 1324 - 1330
(2013/11/19)
-
- Chiral bis(imidazolinyl)phenyl NCN pincer rhodium(III) Catalysts for enantioselective allylation of aldehydes and carbonyl-ene reaction of trifluoropyruvates
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Chiral NCN pincer rhodium(III) complexes with bis(imidazolinyl)phenyl ligands were found to be effective catalysts for the allylation of a variety of electronically and structurally diverse aldehydes with allyltributyltin, giving the corresponding optical
- Wang, Tao,Hao, Xin-Qi,Huang, Juan-Juan,Niu, Jun-Long,Gong, Jun-Fang,Song, Mao-Ping
-
p. 8712 - 8721
(2013/09/24)
-
- Synthetically amenable amide derivatives of tosylated-amino acids as organocatalysts for enantioselective allylation of aldehydes: Computational rationale for enantioselectivity
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A phenylalanine derived chiral amide is developed that serves as an effective organocatalyst for the reaction of allyltrichlorosilane with aryl, hetero-aryl and α,β-unsaturated aldehydes to afford the desired homoallylic alcohols in good yield (up to 90%)
- Ghosh, Debashis,Sahu, Debashis,Saravanan,Abdi, Sayed H. R.,Ganguly, Bishwajit,Khan, Noor-Ul H.,Kureshy, Rukhsana I.,Bajaj, Hari C.
-
supporting information
p. 3451 - 3460
(2013/06/05)
-
- Mechanistic dichotomy in the asymmetric allylation of aldehydes with allyltrichlorosilanes catalyzed by chiral pyridine N-oxides
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Detailed kinetic and computational investigation of the enantio- and diastereoselective allylation of aldehydes 1 with allyltrichlorosilanes 5, employing the pyridine N-oxides METHOX (9) and QUINOX (10) as chiral organocatalysts, indicate that the reaction can proceed through a dissociative (cationic) or associative (neutral) mechanism: METHOX apparently favors a pentacoordinate cationic transition state, while the less sterically demanding QUINOX is likely to operate via a hexacoordinate neutral complex. In both pathways, only one molecule of the catalyst is involved in the rate- and selectivity-determining step, which is supported by both experimental and computational data. Copyright
- Malkov, Andrei V.,Stoncius, Sigitas,Bell, Mark,Castelluzzo, Fabiomassimo,Ramirez-Lopez, Pedro,Biedermannova, Lada,Langer, Vratislav,Rulisek, Lubomir,Kocovsky, Pavel
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p. 9167 - 9185
(2013/07/26)
-
- Synthesis of axially chiral C10-BridgePHOS oxides and their use as organocatalysts in enantioselective allylations of aldehydes
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A series of C10-BridgePHOS oxides possessing different substituted groups on the diphenyl phosphine system were synthesized and tested as organocatalysts in the allylation of aldehydes with allyltrichlorosilane, providing chiral homoallylic alc
- Chen, Jianzhong,Liu, Delong,Fan, Dongyang,Liu, Yangang,Zhang, Wanbin
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p. 8161 - 8168
(2013/09/02)
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- Addition of aldehydes with allyltrichlorosilane catalyzed by chiral bis-N-O secondary amides
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New axially N-oxide amides derived from l-tryptophan were prepared and used as organocatalysts in enantioselective allylation of aromatic aldehydes with allyltrichlorosilanes. The corresponding addition adducts homoallylic chiral alcohols obtained high en
- Deng, Yu,Pan, Wei,Pei, Yu-Ning,Li, Jin-Liang,Bai, Bing,Zhu, Hua-Jie
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p. 10431 - 10437
(2013/11/19)
-
- 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
-
supporting information
p. 4634 - 4637
(2013/10/08)
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- Allylation of aldehydes with potassium allyltrifluoroborate catalyzed by Amberlyst A-15
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The use of the commercially available resin Amberlyst-15 as catalyst for allylation of aldehydes by potassium allyltrifluoroborate is described. The method features the use of a commercially available catalyst, aqueous media, and the products were obtained in high yields, short reaction times, at room temperature and no further purification. The catalyst was recovered and reused up to six times in further allylation reactions without significant yield losses. 11B NMR experiments were conducted in order to evaluate the possible mechanism pathway. The formation of tricoordinate boron species was not observed.
- Couto, Túlio R.,Freitas, Juliano C.R.,Cavalcanti, Italo H.,Oliveira, Roberta A.,Menezes, Paulo H.
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p. 7006 - 7010
(2013/07/26)
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- Allylation of aldehydes with potassium allyltrifluoroborate catalyzed by lanthanide-based metal-organic framework
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The use of the framework [Eu2(fum)3(H 2O)4]·(3H2O), Eu-MOF, as catalyst for allylation of aldehydes by potassium allyltrifluoroborate is described. The method features the use of small catalyst loads and wet solvents, and the products were obtained in high yields, short reaction times, at room temperature with no further purification. The catalyst was recovered and reused up to six times in further allylation reactions without significant loss in the yields.
- Freitas, Juliano C.R.,De Oliveira, Cristiane K.,Cunha, Edilanio C.,Malvestiti, Ivani,Alves Jr., Severino,Longo, Ricardo L.,Menezes, Paulo H.
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supporting information
p. 1558 - 1561
(2013/03/14)
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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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- Bismuth triflate-catalyzed asymmetric allylation of aromatic aldehydes
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Fits the BiL2: A highly enantioselective method for the catalytic allylation of aromatic aldehydes was developed using Bi(OTf) 3 and Trost's (R,R)-ProPhenol ligand (see scheme). Good yields and high enantioselectivities were obtained for a variety of aromatic aldehydes. The disclosed method is the first example of an enantioselective allylation reaction of aldehydes using a chiral BiIII complex. A preliminary characterization of the BiIII pre-catalyst is also reported. Copyright
- Li, Zhiya,Plancq, Baptiste,Ollevier, Thierry
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supporting information; experimental part
p. 3144 - 3147
(2012/04/17)
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- Conformationally rigid chiral pyridine N-oxides as organocatalyst: Asymmetric allylation of aldehydes
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A pyridine unit with a conformationally rigid chiral backbone has been designed and synthesized in an enantiomerically pure form to utilize in the Lewis base-catalyzed Sakurai-Hosomi-Denmark-type allylation reaction. The chiral pyridine N-oxide in 1:1 mix
- Gnanamani, Elumalai,Someshwar, Nagamalla,Ramanathan, Chinnasamy Ramaraj
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supporting information
p. 2101 - 2106
(2012/11/07)
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- Allylation of functionalized aldehydes by potassium allyltrifluoroborate catalyzed by 18-Crown-6 in aqueous media
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An efficient method for the allylation of aldehydes containing a broad range of functional groups using potassium allyltrifluoroborate is described. The reaction utilizes a catalytic amount of 18-C-6 in biphasic media under open atmosphere and room temperature to provide the corresponding homoallylic alcohols in high yields and without the necessity of any subsequent purification.
- Barbosa, Fernanda C. G.,Freitas, Juliano C. R.,Melo, Caio F.,Menezes, Paulo H.,Oliveira, Roberta A.
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p. 14099 - 14110
(2013/02/25)
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- Synthesis and biological evaluation of α,β-unsaturated lactones as potent immunosuppressive agents
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Compounds having α,β-unsaturated lactones display a variety of biological activities. Many research groups have tested both natural and unnatural α,β-unsaturated lactones for as-yet undiscovered biological properties. We synthesized α,β-unsaturated lacton
- Lee, Sun-Mi,Lee, Won-Gil,Kim, Young-Chul,Ko, Hyojin
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supporting information; experimental part
p. 5726 - 5729
(2011/10/18)
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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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- 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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- Homoallylic alcohols via a chemo-enzymatic one-pot oxidation-allylation cascade
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A chemo-enzymatic one-pot, two-step transformation of (hetero)-benzylic and cinnamic alcohols to yield the elongated homoallylic sec-alcohols in water in up to 96% isolated yield has been developed. The sequence comprised an enzymatic alcohol oxidation using galactose oxidase from Fusarium sp. NRRL 2903 to furnish the corresponding aldehydes, which were subjected directly to allylation via indium(0)-mediated Barbier-type coupling with allyl bromide or by addition of allylboronic acid pinacol ester. Copyright
- Fuchs, Michael,Schober, Markus,Pfeffer, Jan,Kroutil, Wolfgang,Birner-Gruenberger, Ruth,Faber, Kurt
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supporting information; experimental part
p. 2354 - 2358
(2011/10/31)
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- C2-symmetrical bipyridyldiols as promising enantioselective catalysts in Nozaki-Hiyama allylation
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Several new chiral bipyridyldiol ligands that promote the chromium-catalyzed enantioselective addition of allylic halides to aldehydes in up to 99% ee were synthesized. The chromium-catalyzed allylation of aldehydes using ligands 4 and 4a in the presence
- Huang, Xin-Ren,Pan, Xin-Hong,Lee, Gene-Hsian,Chen, Chinpiao
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supporting information; experimental part
p. 1949 - 1954
(2011/10/13)
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