- Iridium-catalyzed carbonyl allylation by allyl ethers with tin(II) chloride
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3-Alkoxypropenes, namely allyl ethers such as allyl butyl ether, allyl 2-hydroxypropyl ether, and diallyl ether, serve as reagents for the allylation of aldehydes with tin(II) chloride in the presence of a catalytic amount of [IrCl(cod)]2 in TH
- Masuyama, Yoshiro,Marukawa, Masanori
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- Polymer-supported formamides as reusable organocatalysts for allylation of aldehydes with allyltrichlorosilane
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New types of polymer-supported formamides have been synthesized from chloromethylated resins and formamides; it was found that the polymers worked well as organocatalysts in the allylation of aldehydes with allyltrichlorosilane to afford homoallylic alcoh
- Ogawa, Chikako,Sugiura, Masaharu,Kobayashi, Shu
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- Gallium metal mediated allylation of carbonyl compounds and imines under solvent-free conditions
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Gallium metal is effective in mediating the allylation of various carbonyl compounds and imines under solvent-free conditions, with the application of sonic energy, affording the corresponding homoallylic alcohols and amines. The imines themselves were al
- Andrews, Philip C.,Peatt, Anna C.,Raston, Colin L.
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- AN EFFICIENT SYNTHESIS OF HOMOALLYL ALCOHOLS BY THE REACTION OF ALLYL HALIDES WITH CARBONYL COMPOUNDS IN THE PRESENCE OF METALLIC TIN
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In the presence of metallic tin, allyl halides were found to react smoothly with carbonyl compounds under mild conditions to give the corresponding homoallyl alcohols in good yields.
- Mukaiyama, Teruaki,Harada, Taira
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- Additive effects of ligand activated allylation of aldehydes by allyltrichlorosilane
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The rate of allylation of aldehydes using a combination of allyltrichlorosilane and O-donor ligands can he profoundly accelerated by the addition of a range of simple tetra-n-butylammonium salts. Measured tin values decrease from over 6 hours under define
- Short, Joanne D.,Attenoux, Sandrine,Berrisford, David J.
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- Ruthenium complex catalyzed allylation of aldehydes with allylic acetates
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Ruthenium complexes such as Ru3(CO)12 and RuCl3.nH2O show high catalytic activity in the allylation of aldehydes by allylic acetates at 120 deg C to give homoallylic alcohols in good yields.
- Tsuji, Yasushi,Mukai, Takeshi,Kondo, Teruyuki,Watanabe, Yoshihisa
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- Ni-Catalyzed 1,2-Diarylation of Alkenyl Ketones: A Comparative Study of Carbonyl-Directed Reaction Systems
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A nickel-catalyzed 1,2-diarylation of alkenyl ketones with aryl iodides and arylboronic esters is reported. Ketones with a variety of substituents serve as effective directing groups, offering high levels of regiocontrol. A representative product is diversified into a wide range of useful products that are not readily accessible via existing 1,2-diarylation reactions. Preliminary mechanistic studies shed light on the binding mode of the substrate, and Hammett analysis reveals the effect of electronic factors on initial rates.
- Apolinar, Omar,Derosa, Joseph,Engle, Keary M.,Karunananda, Malkanthi K.,Kleinmans, Roman,Li, Zi-Qi,Tran, Van T.,Wisniewski, Steven R.
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supporting information
p. 5311 - 5316
(2021/07/26)
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- 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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- Bi(cyclopentyl)diol-Derived Boronates in Highly Enantioselective Chiral Phosphoric Acid-Catalyzed Allylation, Propargylation, and Crotylation of Aldehydes
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In this study, we disclose the catalytic addition of bi(cyclopentyl)diol-derived boronates to aldehydes promoted by chiral phosphoric acids, allowing for the formation of enantioenriched homoallylic, propargylic, and crotylic alcohols (up to >99% enantiom
- Yuan, Jinping,Jain, Pankaj,Antilla, Jon C.
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p. 12988 - 13003
(2020/11/23)
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- Axially chiral N,N′-dioxides ethers for catalysis in enantioselective allylation of aldehydes
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A series of axially chiral ethers synthesized from biscarboline N,N′-dioxides, (S)-1a to (S)-1n, was investigated in enantioselectivity addition reactions of allyltrichlorosilane with a series of substituted aldehydes, including bulky substituted aldehydes. High enantioselectivities (up to 96%ee) were achieved using the catalyst (S)-1k at 1 mol % loading.
- Wu, Shijie,Xing, Yongfei,Wang, Jie,Guo, Xingchen,Zhu, Huajie,Li, Wan
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supporting information
p. 947 - 957
(2019/08/30)
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- TetraPh-Tol-BITIOPO: A new atropisomeric 3,3′-bithiophene based phosphine oxide as an organocatalyst in Lewis base-catalyzed Lewis acid mediated reactions
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A new chiral phosphine oxide based on a 3,3′-bithiophene scaffold (TetraPh-Tol-BITIOPO) was synthesized, fully characterized and separated into antipodes through chiral HPLC. This new compound was successfully employed as an organocatalyst in Lewis base-catalyzed Lewis acid mediated reactions involving trichlorosilyl compounds. The new atropisomeric catalyst was able to promote the allylation of aldehydes with allyltrichlorosilane in up to 98% yield and up to 96% enantiomeric excess (ee), and the direct aldol reaction to afford β-hydroxy ketones and β-hydroxy thioesters, with good chemical yields and modest stereochemical efficiency. Computational studies helped to elucidate and to rationalize the stereochemical outcome of the reactions catalyzed by TetraPh-Tol-BITIOPO that was found to favour the formation of the isomer with an opposite absolute configuration in comparison with the products obtained with the previously reported 3,3′-bithiophene-based catalyst.
- Mirco, Abbinante Vincenzo,Maurizio, Benaglia,Sergio, Rossi,Tiziana, Benincori,Roberto, Cirilli,Marco, Pierini
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supporting information
p. 7474 - 7481
(2019/08/20)
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- Synthesis of Enantiomerically Pure 5,6-Dihydropyran-2-ones via Chemoenzymatic Sequential DKR-RCM Reaction
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The enantiomerically pure 5,6-dihydropyran-2-ones play a crucial role as the building blocks in the synthesis of various bioactive compounds. A new straightforward protocol toward enantiomerically pure 5,6-dihydropyran-2-ones based on enzymatic dynamic ki
- Koszelewski, Dominik,Borys, Filip,Brodzka, Anna,Ostaszewski, Ryszard
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supporting information
p. 1653 - 1658
(2019/01/24)
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- 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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- 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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- 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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- Chiral Unsymmetrically Substituted Bipyridine N,N′-Dioxides as Catalysts for the Allylation of Aldehydes
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A series of unsymmetrically substituted diastereoisomeric (Ra,R) and (Sa,R) bipyridine N,N′-dioxides was synthesized by using oxidative coupling of the corresponding metallated tetrahydroisoquinoline N-oxides in the presence of iodin
- Ul?, Jan,Ne?as, David,Koukal, Petr,Havlí?ek, Vojtěch,To?ner, Zdeněk,Hybelbauerová, Simona,Kotora, Martin
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supporting information
p. 5109 - 5116
(2018/07/31)
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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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- 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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- First total synthesis of the highly potent antitumor lactones 8-chlorogoniodiol and parvistone A: Exploiting a bioinspired late-stage epoxide ring-opening
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The first protecting group-free total syntheses of the highly potent antitumor chlorinated styryllactone secondary metabolites 8-chlorogoniodiol, parvistone A, and one analogue 8-epi-parvistone A, have been accomplished from commercially available trans-cinnamaldehyde in five steps with high overall yields. The chlorine-bearing stereogenic center of these silent secondary metabolites was introduced via a bioinspired late-stage regioselective epoxide ring-opening strategy. Maruoka asymmetric allylation, acrylation, ring-closing metathesis and asymmetric epoxidation, greatly facilitate the synthesis of the key intermediates goniothalamin oxide and (6S,7S,8S)-isogoniothalamin oxide.
- Ramesh, Perla,Narasimha Reddy, Yarram,Narendar Reddy, Thatikonda,Srinivasu, Navuluri
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supporting information
p. 246 - 249
(2017/02/15)
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- Asymmetric Allylation of Carbonyl Compounds Catalyzed by a Chiral Phosphine–Silver Complex
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A catalytic, asymmetric allylation reaction of aldehydes or ketones with allyltrimethoxysilane was achieved by using a BINAP·AgBF4 [BINAP = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl] complex as the chiral precatalyst and triethylamine as the
- Yanagisawa, Akira,Yang, Nan,Bamba, Kentaro
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supporting information
p. 6614 - 6618
(2017/12/15)
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- Enantioselective Allyl-, and Allenylboration of Aldehydes Catalyzed by Chiral Hydroxyl Carboxylic Acid
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Asymmetric allylboration of aldehydes with allylboronic acid pinacol ester catalyzed by chiral hydroxyl carboxylic acid is described. This reaction provides synthetically useful homoallyl alcohols in high yield with good to high enantioselectivity. The pr
- Ota, Yuya,Kawato, Yuji,Egami, Hiromichi,Hamashima, Yoshitaka
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supporting information
p. 976 - 980
(2017/05/05)
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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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- Polystyrene-Supported TRIP: A highly recyclable catalyst for batch and flow enantioselective allylation of aldehydes
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The widely applicable TRIP phosphoric acid catalyst has been immobilized on polystyrene using a copolymerization-based strategy. The resin (PS-TRIP) has proven to be highly active and enantioselective in the asymmetric allylboration of aldehydes. Moreover
- Clot-Almenara, Lidia,Rodríguez-Escrich, Carles,Osorio-Planes, Laura,Pericas, Miquel A.
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p. 7647 - 7651
(2018/05/23)
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- Accessing Both Retention and Inversion Pathways in Stereospecific, Nickel-Catalyzed Miyaura Borylations of Allylic Pivalates
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We have developed a stereospecific, nickel-catalyzed Miyaura borylation of allylic pivalates, which delivers highly enantioenriched α-stereogenic γ-aryl allylboronates with good yields and regioselectivities. Our complementary sets of conditions enable access to either enantiomer of allylboronate product from a single enantiomer of readily prepared allylic pivalate substrate. Excellent functional group tolerance, yields, regioselectivities, and stereochemical fidelities are observed. The stereochemical switch from stereoretention to stereoinversion largely depends upon solvent and can be explained by competitive pathways for the oxidative addition step. Our mechanistic investigations support a stereoretentive pathway stemming from a directed oxidative addition and a stereoinvertive pathway that is dominant when MeCN blocks coordination of the directing group by binding the nickel catalyst.
- Zhou, Qi,Srinivas, Harathi D.,Zhang, Songnan,Watson, Mary P.
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supporting information
p. 11989 - 11995
(2016/10/07)
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- Extremely Active Organocatalysts Enable a Highly Enantioselective Addition of Allyltrimethylsilane to Aldehydes
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The enantioselective allylation of aldehydes to form homoallylic alcohols is one of the most frequently used carbon–carbon bond-forming reaction in chemical synthesis and, for several decades, has been a testing ground for new asymmetric methodology. Howe
- Kaib, Philip S. J.,Schreyer, Lucas,Lee, Sunggi,Properzi, Roberta,List, Benjamin
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supporting information
p. 13200 - 13203
(2016/10/30)
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- Biosynthesis-Inspired Total Synthesis of Bioactive Styryllactones (+)-Goniodiol, (6S,7S,8S)-Goniodiol, (-)-Parvistone D, and (+)-Parvistone e
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A protecting-group-free total synthesis of (+)-goniodiol (1), (6S,7S,8S)-goniodiol (2), (-)-parvistone D (4), and (+)-parvistone E (6) was efficiently achieved in five steps from commercially available trans-cinnamaldehyde with high overall yields (72-75%). The synthesis strategy was inspired from the proposed biosynthesis pathway of styryllactones. Key transformations of the strategy include a one-pot conversion of goniothalamin oxide to goniodiol or 9-deoxygoniopypyrone in aqueous media, stereoselective epoxidation, ring-closing metathesis, and stereoselective Maruoka allylation. The route is amenable to synthesis of various analogues for biological evaluation.
- Ramesh, Perla,Rao, Tadikamalla P.
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p. 2060 - 2065
(2016/09/09)
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- Protecting-Group-Free Total Synthesis of 8-Methoxygoniodiol
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A concise stereoselective total synthesis of the naturally occurring styryl lactone 8-methoxygoniodiol in five simple steps from readily available inexpensive trans-cinnamaldehyde is described. The efficient synthesis features a successful protecting-group-free strategy, with desirable step- and atom-economy. The synthetic strategy relies on a Maruoka asymmetric allylation, an epoxidation, a ring-closing metathesis, and a stereoselective epoxide ring opening as key steps.
- Ramesh, Perla
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p. 4300 - 4304
(2016/11/26)
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- DABO Boronate Promoted Conjugate Allylation of α,β-Unsaturated Aldehydes Using Copper(II) Catalysis
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The first catalytic method for the selective 1,4-conjugate allylation of α,β-unsaturated aldehydes is reported. The method employs an air-stable diethanolamine-complexed boronic acid (DABO boronate) as the allyl transfer reagent and promotes conjugate add
- Roest, Pjotr C.,Michel, Nicholas W. M.,Batey, Robert A.
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p. 6774 - 6778
(2016/08/16)
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- Synthesis of Aromatic Retinoids and Curcuminoids and Evaluation of their Antiproliferative, Antiradical, and Anti-inflammatory Activities
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Natural retinoids and curcuminoids are known for their broad spectrum of biological properties, such as antioxidant, anti-inflammatory, antitumor, and so forth. In this work, a convenient synthesis of aromatic retinoids and curcuminoids from vinyl or allyl ketones, and the corresponding alcohols, using olefin metathesis as a key reaction, was elaborated. The best yields and diastereoselectivities were obtained from allylic or homoallylic alcohols by employing the two-step cross-metathesis/oxidation procedure. The synthesized analogues were tested for their antiproliferative activity on human cancer cell lines of various origin (leukemia CEM, adenocarcinoma MCF7, cervical carcinoma HeLa) as well as for their antioxidant and anti-inflammatory activity in vitro. All examined derivatives exhibited strong anti-inflammatory activity in vitro without affecting cell viability. They also showed strong cytotoxicity against leukemia cell line CEM, except for 18 and 35. The antioxidant activity of the tested compounds was rather weak.
- Morzycki, Jacek W.,Rárová, Lucie,Grúz, Ji?i,Sawczuk, Tomasz,Kie?czewska, Urszula,Siergiejczyk, Leszek,Wojtkielewicz, Agnieszka
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p. 339 - 350
(2016/08/19)
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- Total synthesis of cryptomoscatone F1 through an asymmetric aldol approach
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A stereoselective total synthesis of naturally occurring styryl lactone, cryptomoscatone F1 is described. A Mukaiyama asymmetric aldol reaction, Brown's asymmetric allylation, Maruoka asymmetric allylation, and cross metathesis were used as the key steps.
- Ramesh, Perla,Raju, Atla,Fadnavis, Nitin W.
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p. 1251 - 1255
(2015/11/09)
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- Strong Lewis acids of air-stable binuclear triphenylantimony(V) complexes and their catalytic application in C-C bond-forming reactions
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Two air-stable novel Lewis acids of triphenylantimony(V) pentafluorbezenesulfonates (2) and perfluorooctanesulfonates (3) were successfully synthesized and characterized. X-ray studies and thermo-gravimetric analysis found that these complexes showed high anti-hydrolyzability and thermal stability. The high catalytic activity and excellent recyclability of these complexes were achieved in the Michael addition reaction and the allylation reaction. On account of their stability, storability, as well as catalytic efficiency, these complexes should find a broad range of utility in organic synthesis.
- Li, Ningbo,Qiu, Renhua,Zhang, Xiaohong,Chen, Yun,Yin, Shuang-Feng,Xu, Xinhua
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p. 4275 - 4281
(2015/06/08)
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- Stereoselective synthesis of cryptomoscatone D2
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Cryptomoscatone D2 was synthesized stereoselectively from trans-cinnamaldehyde. The synthesis of the triol frame work relied on the creations of the stereocenters independently by utilizing double Maruoka allylations and Sharpless epoxidation. The lactone
- Raju, Atla,Sabitha, Gowravaram
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supporting information
p. 5756 - 5758
(2015/02/18)
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- 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)
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- 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
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supporting information
p. 5266 - 5268
(2015/01/09)
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- Bismuth chloride mediated allylation of carbonyl compounds in aqueous media: A mechanistic investigation
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The bismuth chloride mediated, aluminum promoted aqueous Barbier type coupling of allyl unit with carbonyl compounds which gives the corresponding homoallyl alcohol is studied. The transient in situ generated allylbismuth(III) bromide intermediate was stu
- Jadhav,Pardeshi
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p. 4948 - 4952
(2014/12/11)
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- 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
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p. 8712 - 8721
(2013/09/24)
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- Facile chemoselective carbonyl allylation of chalcones with allyltributylstannane catalyzed by CuI
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Chemoselective allylation of carbonyl functionality of chalcones with allyltributylstannane was accomplished in the presence of CuI as catalyst. This reaction works well in DMF at 70 C with exclusive formation of 1,2-addition product. Interesting feature
- Kalita, Pabitra Kumar,Phukan, Prodeep
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p. 4442 - 4445
(2013/07/26)
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- Br?nsted acid-catalyzed asymmetric allylation and propargylation of aldehydes
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A method synthesizing homoallylic or homopropargylic alcohols was developed to react aldehydes with allyl boronates, such as allylboronic acid pinacol ester, or allenylborates in the presence of a catalytic amount of a chiral binaphthyl-derived chiral pho
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Page/Page column 8; 19; 20
(2013/08/28)
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- Stereospecific allyl-aryl coupling catalyzed by in situ generated palladium nanoparticles in water under ambient conditions
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A practical process for the stereospecific cross-coupling of secondary allylic carbonates with arylboronic acids has been developed. The reaction is catalyzed by in situ generated palladium nanoparticles (PdNPs) without any ligands and additional stabilizers in water under ambient conditions and furnishes the allyl-aryl coupling products in high isolated yields with high stereospecificities as well as excellent chemo-, regio- and E/Z-selectivities. The in situ generated PdNPs showed extraordinary catalytic activity (S/C up to 5000) even for the allyl-aryl coupling reactions of easily eliminated allylic carbonates under aqueous ambient conditions. The mechanism of the process has also been investigated.
- Zhao, Jingming,Ye, Jiang,Zhang, Yong Jian
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supporting information
p. 491 - 498
(2013/05/09)
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- 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.
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supporting information
p. 3451 - 3460
(2013/06/05)
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- Porous and robust lanthanide metal-organoboron frameworks as water tolerant Lewis acid catalysts
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Porous and robust 12-connected metal-organic frameworks (MOFs) were constructed by linking tetranuclear lanthanide (Ln) carbonate clusters with organoboron-derived tricarboxylate bridging ligands. The high-connectivity Ln-MOFs feature remarkable thermal a
- Liu, Yan,Mo, Ke,Cui, Yong
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supporting information
p. 10286 - 10291
(2013/10/01)
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- 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
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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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- 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)
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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)
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- Rapid synthesis of homoallylic alcohol from aldehyde with allyltributylstannane under solvent-free conditions
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A catalytic amount (2 mol %) of phosphotungstic acid (PTA) is sufficient to synthesize homoallylic alcohol in excellent yields from aldehyde with allyltributylstannane upon grinding under solvent-free reaction conditions. Easy handling, very short reactio
- Bora, Pranjal P.,Sema, H. Atoholi,Wahlang, Barisha,Bez, Ghanashyam
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experimental part
p. 167 - 172
(2012/03/07)
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- Consecutive iridium catalyzed C-C and C-H bond forming hydrogenations for the diastereo- and enantioselective synthesis of syn-3-fluoro-1-alcohols: C-H (2-fluoro)allylation of primary alcohols
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Commercially available (2-fluoro)allyl chloride serves as an efficient allyl donor in highly enantioselective iridium catalyzed carbonyl (2-fluoro)allylations from the alcohol or aldehyde oxidation level via transfer hydrogenation. Diastereoselective Crab
- Hassan, Abbas,Montgomery, T. Patrick,Krische, Michael J.
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supporting information; experimental part
p. 4692 - 4694
(2012/06/01)
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- Asymmetric allylboration of aldehydes with pinacol allylboronates catalyzed by 1,1′-spirobiindane-7,7′-diol (SPINOL) based phosphoric acids
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The asymmetric allylboration of aldehydes with pinacolallylboronates catalyzed by 1,1′-spirobiindane-7,7′-diol (SPINOL) based phosphoric acids is described. 6,6′-Bis(2,4,6-triisopropylphenyl)SPINOL-based phosphoric acid was found to be a general, highly e
- Xing, Chun-Hui,Liao, Yuan-Xi,Zhang, Yimei,Sabarova, Darya,Bassous, Monica,Hu, Qiao-Sheng
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supporting information; experimental part
p. 1115 - 1118
(2012/04/10)
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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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- Strong Lewis acids of air-stable metallocene bis(perfluorooctanesulfonate)s as high-efficiency catalysts for carbonyl-group transformation reactions
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Strong Lewis acids of air-stable metallocene bis(perfluorooctanesulfonate)s [M(Cp)2][OSO2C8F17] 2·nH2O·THF (M=Zr (2 a·3 H 2O·THF), M=Ti (2 b·2 H2O·THF)) were synthesized by the reaction of [M(Cp)2]Cl2 (M=Zr (1 a), M=Ti (1 b)) with nBuLi and C8F17SO3H (2 equiv) or with C8F17SO3Ag (2 equiv). The hydrate numbers (n) of these complexes were variable, changing from 0 to 4 depending on conditions. In contrast to well-known metallocene triflates, these complexes suffered no change in open air for a year. thermogravimetry-differential scanning calorimetry (TG-DSC) analysis showed that 2 a and 2 b were thermally stable at 300 and 180 °C, respectively. These complexes exhibited unusually high solubility in polar organic solvents. Conductivity measurement showed that the complexes (2 a and 2 b) were ionic dissociation in CH3CN solution. X-ray analysis result confirmed 2 a·3 H2O·THF was a cationic organometallic Lewis acid. UV/Vis spectra showed a significant red shift due to the strong complex formation between 10-methylacridone and 2 a. Fluorescence spectra showed that the Lewis acidity of 2 a fell between those of Sc3+ (λem=474 nm) and Fe3+ (λem=478 nm). ESR spectra showed the Lewis acidity of 2 a (0.91 eV) was at the same level as that of Sc3+ (1.00 eV) and Y 3+ (0.85 eV), while the Lewis acidity of 2 b (1.06 eV) was larger than that of Sc3+ (1.00 eV) and Y3+ (0.85 eV). They showed high catalytic ability in carbonyl-compound transformation reactions, such as the Mannich reaction, the Mukaiyama aldol reaction, allylation of aldehydes, the Friedel-Crafts acylation of alkyl aromatic ethers, and cyclotrimerization of ketones. Moreover, the complexes possessed good reusability. On account of their excellent catalytic efficiency, stability, and reusability, the complexes will find broad catalytic applications in organic synthesis. Copyright
- Qiu, Renhua,Xu, Xinhua,Peng, Lifeng,Zhao, Yalei,Li, Ningbo,Yin, Shuangfeng
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supporting information; experimental part
p. 6172 - 6182
(2012/06/30)
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- Chemoenzymatic synthesis of a mixed phosphine-phosphine oxide catalyst and its application to asymmetric allylation of aldehydes and hydrogenation of alkenes
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The chemoenzymatic synthesis of a Lewis basic phosphine-phosphine oxide organocatalyst from a cis-dihydrodiol metabolite of bromobenzene proceeds via a palladium-catalysed carbon-phosphorus bond coupling and a novel room temperature Arbuzov [2,3]-sigmatropic rearrangement of an allylic diphenylphosphinite. Allylation of aromatic aldehydes were catalysed by the Lewis basic organocatalyst giving homoallylic alcohols in up to 57% ee. This compound also functioned as a ligand for rhodium-catalysed asymmetric hydrogenation of acetamidoacrylate giving reduction products with ee values of up to 84%.
- Boyd, Derek R.,Bell, Mark,Dunne, Katherine S.,Kelly, Brian,Stevenson, Paul J.,Malone, John F.,Allen, Christopher C. R.
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experimental part
p. 1388 - 1395
(2012/03/27)
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- Sequencing cross-metathesis and non-metathesis reactions to rapidly access building blocks for synthesis
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The olefin cross-metathesis reaction has been sequenced with four common organic transformations in a one- or two-pot manner to rapidly access useful building blocks. Those reactions are: (1) phosphorus-based olefination (e.g., Wittig and Horner-Wadsworth-Emmons); (2) hydride reduction; (3) Evans propionate aldol reaction; (4) Brown allyl- and Roush crotyl-boration. The products of these reactions include stereodefined 2,4-dienoates, trans allylic alcohols, syn-propionate aldols, and chiral non-racemic homoallylic alcohols, respectively. Many of these intermediates have been carried further to natural products, demonstrating the utility of the methodology.
- Sirasani, Gopal,Paul, Tapas,Andrade, Rodrigo B.
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experimental part
p. 2197 - 2205
(2011/04/22)
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- A one-pot oxidation/allylation/oxidation sequence for the preparation of β,γ-unsaturated ketones directly from primary alcohols
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A one-pot oxidation/allylation/oxidation procedure has been developed for the conversion of primary alcohols into β,γ-unsaturated ketones. The methodology has been applied to a range of alcohols, and in some cases, isomerisation to produce the corresponding α,β-unsaturated ketones has been carried out.
- Moody, Catherine L.,Pugh, David S.,Taylor, Richard J.K.
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p. 2511 - 2514
(2011/05/09)
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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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p. 2354 - 2358
(2011/10/31)
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- Electrochemical allylation of aldehydes in a solvent-free cavity cell with a graphite powder cathode
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Mixtures of carbonyl compounds and allyl halides, adsorbed on a graphite powder cathode, were reduced under aqueous anolyte to give high yields of homoallylic alcohols. Catalytic amounts of silver or tetrabutylammonium tetrafluoroborate improved the yields significantly. Inexpensive allyl chloride gave superior results when compared to allyl bromide.
- De Souza, Ronny F. M.,Areias, Madalena C. C.,Bieber, Lothar W.,Navarro, Marcelo
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experimental part
p. 1118 - 1120
(2011/06/27)
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- First example of hydrolytic kinetic resolution of acrylate of secondary alcohols by lipase Amano AK
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Lipase Amano AK is found to be extremely efficient catalyst for hydrolytic kinetic resolution of acrylates of secondary alcohols in aqueous phosphate buffer at pH 7.0. Both aliphatic and benzylic secondary alcohols show good to excellent E values.
- Bora, Pranjal P.,Bez, Ghanashyam,Anal, Jasha Momo H.
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experimental part
p. 270 - 275
(2012/07/03)
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