- Uncovering Key Structural Features of an Enantioselective Peptide-Catalyzed Acylation Utilizing Advanced NMR Techniques
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We report on a detailed NMR spectroscopic study of the catalyst-substrate interaction of a highly enantioselective oligopeptide catalyst that is used for the kinetic resolution of trans-cycloalkane-1,2-diols via monoacylation. The extraordinary selectivity has been rationalized by molecular dynamics as well as density functional theory (DFT) computations. Herein we describe the conformational analysis of the organocatalyst studied by a combination of nuclear Overhauser effect (NOE) and residual dipolar coupling (RDC)-based methods that resulted in an ensemble of four final conformers. To corroborate the proposed mechanism, we also investigated the catalyst in mixtures with both trans-cyclohexane-1,2-diol enantiomers separately, using advanced NMR methods such as T1relaxation time and diffusion-ordered spectroscopy (DOSY) measurements to probe molecular aggregation. We determined intramolecular distance changes within the catalyst after diol addition from quantitative NOE data. Finally, we developed a pure shift EASY ROESY experiment using PSYCHE homodecoupling to directly observe intermolecular NOE contacts between the trans-1,2-diol and the cyclohexyl moiety of the catalyst hidden by spectral overlap in conventional spectra. All experimental NMR data support the results proposed by earlier computations including the proposed key role of dispersion interaction.
- Procházková, Eli?ka,Kolmer, Andreas,Ilgen, Julian,Schwab, Mira,Kaltschnee, Lukas,Fredersdorf, Maic,Schmidts, Volker,Wende, Raffael C.,Schreiner, Peter R.,Thiele, Christina M.
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p. 15754 - 15759
(2016/12/16)
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- Functionality, Effectiveness, and Mechanistic Evaluation of a Multicatalyst-Promoted Reaction Sequence by Electrospray Ionization Mass Spectrometry
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A multicatalytic three-step reaction consisting of epoxidation, hydrolysis, and enantioselective monoacylation of cyclohexene was studied by using mass spectrometry (MS). The reaction sequence was carried out in a one-pot reaction using a multicatalyst. All reaction steps were thoroughly analyzed by electrospray ionization (ESI) MS (and MS/MS), as well as high-resolution MS for structure elucidation. These studies allow us to shed light on the individual mode of action of each catalytic moiety. Thus, we find that under the epoxidation conditions, the catalytically active N-methyl imidazole for the terminal acylation step is partially deactivated through oxidation. This observation helps to explain the lower efficiency of the catalyst in the last step compared to the monoacylation performed separately. All reactive intermediates and products of the reaction sequence, as well as of the side-reactions, were monitored, and we present a working mechanism of the reaction.
- Alachraf, M. Wasim,Wende, Raffael C.,Schuler, S?ren M. M.,Schreiner, Peter R.,Schrader, Wolfgang
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p. 16203 - 16208
(2015/11/03)
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- A photoinduced cyclization cascade - Total synthesis of (-)-leuconoxine
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A protecting-group-free and enantioselective total synthesis of the monoterpenoid indole alkaloid (-)-leuconoxine was accomplished. The key step comprises a novel photoinduced domino macrocyclization/transannular cyclization involving the Witkop cyclization, for which additional mechanistic evidence is provided. This process furnishes a diaza[5.5.6.6]fenestrane skeleton, which is a hitherto unprecedented structure element.
- Pfaffenbach, Magnus,Gaich, Tanja
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p. 6355 - 6357
(2015/04/22)
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- Alcohol cross-coupling for the kinetic resolution of diols via oxidative esterification
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We present an organocatalytic C-O-bond cross-coupling strategy to kinetically resolve racemic diols with aromatic and aliphatic alcohols, yielding enantioenriched esters. This one-pot protocol utilizes an oligopeptide multicatalyst, m-CPBA as the oxidant, and N,N-diisopropylcarbodiimide as the activating agent. Racemic acyclic diols as well as trans-cycloalkane-1,2-diols were kinetically resolved, achieving high selectivities and good yields for the products and recovered diols.
- Hofmann, Christine,Schümann, Jan M.,Schreiner, Peter R.
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p. 1972 - 1978
(2015/02/19)
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- Highly enantioselective organocatalytic oxidative kinetic resolution of secondary alcohols using chiral alkoxyamines as precatalysts: Catalyst structure, active species, and substrate scope
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The development and characterization of enantioselective organocatalytic oxidative kinetic resolution (OKR) of racemic secondary alcohols using chiral alkoxyamines as precatalysts are described. A number of chiral alkoxyamines have been synthesized, and their structure-enantioselectivity correlation study in OKR has led us to identify a promising precatalyst, namely, 7-benzyl-3-n-butyl-4-oxa-5-azahomoadamantane, which affords various chiral aliphatic secondary alcohols (ee up to >99%, krel up to 296). In a mechanistic study, chlorine-containing oxoammonium species were identified as the active species generated in situ from the alkoxyamine precatalyst, and it was revealed that the chlorine atom is crucial for high reactivity and enantioselectivity. The present OKR is the first successful example applicable to various unactivated aliphatic secondary alcohols, including heterocyclic alcohols with high enantioselectivity, the synthetic application of which is demonstrated by the synthesis of a bioactive compound.
- Murakami, Keiichi,Sasano, Yusuke,Tomizawa, Masaki,Shibuya, Masatoshi,Kwon, Eunsang,Iwabuchi, Yoshiharu
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supporting information
p. 17591 - 17600
(2015/02/19)
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- Organocatalytic asymmetric hydrolysis of epoxides
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The hydrolytic ring opening of epoxides is an important biosynthetic transformation and is also applied industrially. We report the first organocatalytic variant of this reaction, exploiting our recently discovered activation of carboxylic acids with chiral phosphoric acids via heterodimerization. The methodology mimics the enzymatic mechanism, which involves an enzyme-bound carboxylate nucleophile. A newly designed phosphoric acid catalyst displays high stereocontrol in the desymmetrization of meso-epoxides. The methodology shows wide generality with cyclic, acylic, aromatic, and aliphatic substrates. We also apply our method in the first highly enantioselective anti-dihydroxylation of simple olefins.
- Monaco, Mattia Riccardo,Prevost, Sebastien,List, Benjamin
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p. 8142 - 8145
(2014/08/18)
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- Lipophilic oligopeptides for chemo- and enantioselective acyl transfer reactions onto alcohols
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Inspired by the extraordinary selectivities of acylases, we envisioned the use of lipophilic oligopeptidic organocatalysts for the acylative kinetic resolution/desymmetrization of rac- and meso-cycloalkane-1,2-diols. Here we describe in a full account the discovery and development process from the theoretical concept to the final catalyst, including scope and limitations. Competition experiments with various alcohols and electrophiles show the full potential of the employed oligopeptides. Additionally, we utilized NMR and IR-spectroscopic methods as well as computations to shed light on the factors responsible for the selectivity. The catalyst system can be readily modified to a multicatalyst by adding other catalytically active amino acids to the peptide backbone, enabling the stereoselective one-pot synthesis of complex molecules from simple starting materials.
- Mueller, Christian E.,Zell, Daniela,Hrdina, Radim,Wende, Raffael C.,Wanka, Lukas,Schuler, Soeren M. M.,Schreiner, Peter R.
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p. 8465 - 8484
(2013/09/24)
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- Stereochemical study on an oxygen-directed olefin oxidation and subsequent oxygen cyclization: Differences between peracid and metal oxide-catalyzed hydroperoxide in oxidation reactions
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Optically active (2S,4R)-2-hydroxy-4-pentyl enol ether was prepared for the first time and subjected to hydroxy-directed oxidations at the olefinic group. Treatment with m-chloroperbenzoic acid and tert-butyl hydroperoxide/vanadium acetylacetonate resulte
- Inoue, Aya,Misaki, Tomonori,Fujita, Morifumi,Okuyama, Tadashi,Sugimura, Takashi
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p. 833 - 837
(2013/08/23)
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- Enantiomerically enriched trans-diols from alkenes in one pot: A multicatalyst approach
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Multicatalysts consisting of non-natural oligopeptides with distinctly different catalytic moieties create molecular complexity in a multistep one-pot sequence starting from simple alkenes yielding highly enantiomerically enriched trans-diols. The Royal Society of Chemistry 2012.
- Hrdina, Radim,Mueller, Christian E.,Wende, Raffael C.,Wanka, Lukas,Schreiner, Peter R.
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supporting information; experimental part
p. 2498 - 2500
(2012/04/10)
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- A multicatalyst system for the one-pot desymmetrization/oxidation of meso-1,2-alkane diols
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Two is better than one: We demonstrate the viability of an organocatalytic reaction sequence along a short peptide backbone that carries two independent catalytic functionalities, which allow the rapid, one-pot acylative desymmetrization and oxidation of meso-alkane-1,2-diols to the corresponding acetylated acetoins with good yields and enantioselectivities (see scheme). Copyright
- Mueller, Christian E.,Hrdina, Radim,Wende, Raffael C.,Schreiner, Peter R.
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supporting information; experimental part
p. 6309 - 6314
(2011/08/07)
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- Kinetic resolution of trans-cycloalkane-1,2-diols via Steglich esterification
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We describe the efficient and highly enantioselective kinetic resolution of trans-cycloalkane-1,2-diols utilizing an enantioselective Steglich reaction with a variety of carboxylic acids that form the corresponding anhydrides in situ.
- Hrdina, Radim,Mueller, Christian E.,Schreiner, Peter R.
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supporting information; experimental part
p. 2689 - 2690
(2010/07/08)
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- One-Pot desymmetrization of meso-l,2-hydrocarbon diols through acylation and oxidation
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Avoid racemization! Short lipophilic oligopeptides utilizing nucleophilic N-jt-methyl histidine residues catalyze the desymmetrization of wieso-l,2-diols with enantiomeric ratios of up to 94:6. Direct one-pot oxidation, which avoids the well-known racemiz
- Mueller, Christian E.,Zell, Daniela,Schreiner, Peter R.
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supporting information; experimental part
p. 9647 - 9650
(2010/04/28)
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- Enantioselective kinetic resolution of trans-cycloalkane-1,2-diols
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Finally! The title resolution is achieved with a nonnatural, partially rigid, lipophilic tetrapeptide at low catalyst loadings without additional base or cosolvents. The transition-state model (ball-and-stick model in the scheme; C gray, N blue, O red) emphasizes the interplay between hydrogen-bonding and hydrophobic interactions. (Chemical Equation Presented)
- Mueller, Christian E.,Wanka, Lukas,Jewell, Kevin,Schreiner, Peter R.
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supporting information; experimental part
p. 6180 - 6183
(2009/04/06)
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- Hydroxyselanylation of acyloxycyclohex-3-enes
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In contrast to the corresponding hydroxyiodination reactions, the reaction of acetoxycyclohex-2-ene 1 with N-PSP in the presence of water shows little regiocontrol, but is highly diastereoselective. However, the same reaction of the (R)-phenylglycinate de
- Sweeney,Haughan, Alan F.,Knight,Thobhani, Smita
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p. 2729 - 2737
(2007/10/03)
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- Opening of epoxide rings catalyzed by niobium pentachloride
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The behavior of several epoxides when treated with NbCl5 was studied. In general, the studied epoxides reacted rapidly with NbCl5, giving, in most cases, more than one product (chlorohydrins, products containing solvent residues, as well as rearrangement products). A detailed study was performed to verify the effects of the temperature (rt, 0°C, or -78°C) and of the NbCl5 molar concentration on the composition of the products, yield, and time required for the reactions. Copyright Taylor & Francis Group, LLC.
- Constantino, Mauricio Gomes,Lacerda Jr., Valdemar,Invernize, Paulo Roberto,Filho, Luiz Carlos Da Silva,Da Silva, Gil Valdo Jose
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p. 3529 - 3539
(2008/03/13)
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- Aerobic oxidation of alkenes to esters of vicinal diols with a syn-configuration catalyzed by I2 and the H5PV 2Mo10O40 polyoxometalate
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A new method for the synthesis of vicinal diols from alkenes has been developed. Reaction of molecular iodine in the presence of a polyoxometalate as oxidation catalyst under aerobic conditions in acetic acid solvent leads to the oxidative iodoacetoxylation of an alkene, i.e. formation of a 1,2-iodoacetate. Further in situ substitution of the iodide by water yields the 1,2-diol monoacetate with a predominantly (ca. 4.5:1) cis-configuration. Further esterification under the reaction's acidic conditions leads also to the cis-diacetate. The method may be valuable for the synthesis of cis-vicinal diols without use of toxic osmium catalysts. Georg Thieme Verlag Stuttgart.
- Branytska, Olena,Neumann, Ronny
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p. 2525 - 2527
(2007/10/03)
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- A new synthesis of cis-diol from alkene using iodine-ammonium cerium(IV) nitrate
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The reaction mixtures of 5α-cholest-2-ene with iodine-ammonium cerium(IV) nitrate [CAN(IV)] were converted with potassium hydroxide in methanol-water to give the more hindered 2β,3β-diol in high yield. Cyclohexene and cycloheptene similarly reacted to the corresponding cis-diols in good yield. It was found that this reaction intermediate proceeds to give trans-iodoacetate via trans-iodonitrate. This new synthetic method provided several advantages over the Prevost reaction. Georg Thieme Verlag Stuttgart.
- Horiuchi, C. Akira,Dan, Gong,Sakamoto, Masaki,Suda, Kazuhiko,Usui, Shigeru,Sakamoto, Okihiko,Kitoh, Shinya,Watanabe, Satoshi,Utsukihara, Takamitsu,Nozaki, Sukekatsu
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p. 2861 - 2864
(2007/10/03)
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- Kinetic resolution of trans-2-acetoxycycloalkan-1-ols by lipase-catalysed enantiomerically selective acylation
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Kinetic resolution of a series of racemic trans-cycloalkane-1,2-diol monoacetates rac-2a-d was performed by enantiomerically selective transesterification with vinyl acetate catalysed by commercial and our own-prepared fungal lipases to yield diacetates (
- Bodai, Viktoria,Orovecz, Oliver,Szakacs, Gyoergy,Novak, Lajos,Poppe, Laszlo
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p. 2605 - 2612
(2007/10/03)
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- A one-step procedure for the monoacylation of symmetrical 1,2-diols
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A series of lanthanide (III) salts have been shown to catalyze the monoacylation of symmetrical 1,2-diols by carboxylic acid anhydrides with surprisingly high selectivity.
- Clarke, Paul A.,Kayaleh, Nadim E.,Smith, Martin A.,Baker, James R.,Bird, Stephan J.,Chan, Chuen
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p. 5226 - 5231
(2007/10/03)
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- Asymmetric Hydrolyses of 1,2-Diacetoxycyclohexanes by the Cultured Suspension Cells of Marchantia polymorpha
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The enantioselectivity in the hydrolyses of cis- and trans-1,2-diacetoxycyclohexanes by the cultured suspension cells of Marchantia polymorpha was very high.The acetoxyl groups at the stereogenic center of (R)-configuration were preferentially hydrolyzed.
- Gotoh, Shisei,Aoki, Masahiro,Iwaeda, Tomoko,Izumi, Shunsuke,Hirata, Toshifumi
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p. 1519 - 1520
(2007/10/02)
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- Hydroxyselenation of acetoxycyclohex-2-ene
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The reaction of acetoxycyclohexene with N-phenylselenophthalimide in the presence of water is non-regiospecific, in contrast to the previously reported chloroselenation reaction.
- Haughan, Alan F.,Knight,Sweeney
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p. 1781 - 1784
(2007/10/02)
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- Diastereospecific Hydroxyiodination of 1-Acetoxycyclohex-2-ene via Intramolecular Delivery of Oxygen
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The previously unreported reaction of N-iodosuccinimide with acetoxycyclohex-2-ene to give monoacetates of 3-iodocyclohexane-1,2-diols is diastereospecific.
- Bange, Johannes,Haughan, Alan F.,Sweeney, J. B.
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p. 1405 - 1408
(2007/10/02)
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- Regio- and stereoselective transacylation of polyhydric alcohols using pronase in organic solvents
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Pronase a mixture of proteases from Streptomyces griseus has been found to be a good catalyst for transacylation in organic solvents.With equimolar concentrations of p-nitrophenyl acetate as acyl donor in pyridine, aliphatic diols give predominantly the monoacetates.Glucose and isomeric hexoses give the 6-O-acetates in good yield. 6-Deoxy-sugars however, yield mixtures of acetates indicating that regioselectivity among the secondary hydroxyl groups are poor.Racemic trans-1,2-cyclohexanediol affords the (1R, 2R)-monoacetate in 44percent yield with greater than 90percent enantiomer ic purity. cis-1,2-cyclohexanediol and cis-1,2-cyclohexanedimethanol also give optically active monoacetates.
- Bhattacharya, A,Ali, E
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p. 898 - 899
(2007/10/02)
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- An Optimized Sequential Kinetic Resolution of trans-1,2-Cyclohexanediol
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Quantitative analysis of sequential kinetic resolutions (resolutions that proceed via two or more enantioselective steps) indicates that optimal reinforcement of the enantioselectivities occurs when the rates of the two steps are equal.Unter these conditions, the reinforcement is multiplicative and the overall enantioselectivity, ET(max), is given approximately by 1E2)>/2.To test these ideas we optimized the resolution of trans-1,2-cyclohexanediol, 1.The first step of the porcine liver esterase (PLE) catalyzed hydrolysis of trans-1,2-diacetoxycyclohexane proceeded 47 times faster than the second step and the resolution yielded 1 with only 58 percent ee at 44 molpercent.Addition of a hexane phase slowed the first step by selectively extracting the fast-reaction 1-diacetate (relative rate = 6) and increased the enantiomeric purity to 94 percent ee at 34 molpercent.The resolution of 1 was further improved using lipase from Pseudomonas cepacia (Amano P, PCL) which showed an ET(max) of >2000 as compared to an ET(max) for PLE of 54.Resolution with PCL after equalization of the rates of the two steps gave (R)-1 and recovered (S)-1-diacetate both with >99 percent ee.
- Caron, Gaetan,Kazlauskas, Romas J.
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p. 7251 - 7256
(2007/10/02)
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- Enzymatic Preparation of Optically Pure trans-1,2-Cycloalkanediols
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trans-1,2-Cycloalkanediols (R,R)-1,4 and (S,S)-1,3 of high optical purities are prepared by enzymatic hydrolysis and estrification catalyzed by a lipase from Pseudomonas sp. (SAM II).
- Seemayer, R.,Schneider, M. P.
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- Asymmetric conjugate addition of organometallic reagents to chiral α,β-unsaturated esters
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Asymmetric conjugate addition to α,β-unsaturated ester was studied using four kinds of cyclic diols (1c-4c) as chiral auxiliaries. Among the tested substrates, (R,R)-cyclohexane-1,2-diol derivatives (6a-c) and (1R,2S)-2-hydroxymethylcyclopentanol derivative (7a) showed high and reverse diastereoselectivity in conjugate addition by organocuprates (R2CuLi) and/or Grignard reagents in the presence of copper iodide (RMgBr + CuI), respectively.
- Fang,Ogawa,Suemune,Sakai
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p. 389 - 398
(2007/10/02)
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- A New Alkoxyiodination and Nitratoiodination of Olefins Using Iodine-Cerium(IV) Ammonium Nitrate
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Reactions of cycloolefins with iodine-cerium(IV) ammonium nitrate in alcohols (methanol, ethanol, 1-propanol, and 2-propanol) under reflux gave the corresponding vicinal alkoxyiodocycloalkanes in good yields.In the case of t-butyl alcohol, trans-iodo nitr
- Horiuchi, C. Akira,Nishio, Yoshihiko,Gong, Dan,Fujisaki, Takanori,Kiji, Shinji
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p. 607 - 610
(2007/10/02)
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- Enantiomerically Pure Cyclohexanols and Cyclohexane-1,2-Diol Derivatives; Chiral Auxiliaries and Substitutes for (-)-8-Phenylmenthol. A Facile Enzymatic Route
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A number of optically active cyclohexanol and cyclohexane-1,2-diol derivatives, chiral auxiliaries and substitutes for (-)- and (+)-8-phenylmenthol, have been prepared by enzymatic hydrolysis of their racemic acetates and chloroacetates in the presence of a highly selective ester hydrolase from Pseudomonas sp. (SAM-II).
- Laumen, Kurt,Breitgoff, Detlef,Seemayer, Robert,Schneider, Manfred P.
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p. 148 - 150
(2007/10/02)
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- OXIDATION OF ISOXAZOLINES BY PERACIDS - A USEFUL ROUTE TO β-HYDROXY KETONES AND ACYLATED DIOLS
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A method for bringing about the ring cleavage of isoxazolines by the use of peracids is described.
- Park, Pyeong-uk,Kozikowski, Alan P.
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p. 6703 - 6706
(2007/10/02)
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- An Insight into Enantioselective Hydrolyses of Cyclic Acetates Catalysed by Pseudomonas Fluorescens Lipase
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Hydrolysis of racemic acetates with Pseudomonas fluorescens lipase (PFL) afforded optically active alcohols with the R-configuration, independent of ring size; a three-site model for PFL-catalysed hydrolysis is proposed.
- Xie, Zhuo-Feng,Nakamura, Izumi,Suemune, Hiroshi,Sakai, Kiyoshi
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p. 966 - 967
(2007/10/02)
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- Enzymatic Hydrolysis of (+/-)-trans-1,2-Diacetoxycycloalkanes. A Facile Route to Optically-active Cycloalkane-1,2-diols
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The racemic title compounds were resolved conveniently into the enantiomers with high optical purities by enzymatic hydrolysis in the presence of porcine liver esterase.
- Crout, David H. G.,Gaudet, Veronique S. B.,Laumen, Kurt,Schneider, Manfred P.
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p. 808 - 810
(2007/10/02)
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- DOMINANT cis-DIACETOXYLATION OF ALKENES WITH TELLURIUM(IV) OXIDE AND LITHIUM BROMIDE IN ACETIC ACID
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Oxidation of alkenes with tellurium(IV) oxide and lithium bromide in acetic acid affords the corresponding α,β-diacetoxyalkanes in good yields after acetylation of the primary products with acetic anhydride/pyridine.From cyclic alkenes such as cyclopentene, cyclohexene, cycloheptene, and 1,4-cyclohexadiene, the cis-diacetate is obtained as almost the sole product.In the cases of linear cis alkenes such as cis-2-octene and cis-4-octene cis-stereochemistry is also preferred (cis/trans = 87-89/13-11), while the proportion of the cis-product is decreased in the cases of the corresponding trans-alkenes (cis/trans = 56-58/44-42).Transformation of a C-Te bond to a C-OAc bond under these reaction conditions is shown unambiguously by using β-chloroalkyltellurium(IV) trichlorides (TeCl4 adducts of alkenes) and β-oxyalkyl phenyl tellurides (oxytellurenylation products of alkenes), cis-diacetates being solely formed from the trans-tellurium compounds in a cyclohexyl system.One of the possible reaction patways for the oxidation is proposed which involves the acetoxy-, hydroxy-, and/or halogeno-tellurinylation of a double bond followed by an SN2 type acetolysis of the produced C-Te bond.
- Uemura, Sakae,Ohe, Kouichi,Fukuzawa, Shin-Ichi,Patil, Suresh R.,Sugita, Nobuyuki
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- STUDIES ON THE SYNTHESIS OF HETEROCYCLIC COMPOUNDS. IX. SEPARATION OF DIASTEREOMERIC DIOL COMPOUNDS
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The separation of diastereomeric diols by transformation into the corresponding dioxastannolanes was carried out.The products are solid, stable and easily separable by fractional crystallization.By reaction of acids (or acyl halides) with the stannolanes the corresponding diols (or esters) were obtained in a high degree of purity.The structures of the compounds prepared were assigned on the basis of their analytical, physical and spectral data.
- Anchisi, Carlo,Maccioni, Antonio,Maccioni, Anna Maria,Podda, Gianni
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- Oxidative Displacement of Hypervalent Iodine from Alkyl Iodides
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Oxidative displacement of iodine from primary alkyl iodides and vic-substituted iodocyclohexanes with m-chloroperbenzoic acid in either dichloromethane or t-butyl alcohol-water gives primary alcohols and vic-substituted cyclohexanols, respectively.Retention of configuration at the displacement centre occurs for all of the trans-vic-substituted iodocyclohexanes except the iodoacetate and iodotrifluoroacetate where inversion of configuration occurs to give cis-hydroxy-esters.Oxidation of (S)-2-iodo-octane occurs with almost complete inversion to give (R)-octan-2-ol but also affords octan-1-ol, octan-3-ol, and octan-2-one.
- Cambie, Richard C.,Chambers, David,Lindsay, Barry G.,Rutledge, Peter S.,Woodgate, Paul D.
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p. 822 - 827
(2007/10/02)
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