53723-52-7Relevant academic research and scientific papers
The total syntheses of basiliolide C, epi-basiliolide C, and protecting-group-free total syntheses of transtaganolides C and D
Gordon, Jonny R.,Nelson, Hosea M.,Virgil, Scott C.,Stoltz, Brian M.
, p. 9740 - 9747 (2014)
The total syntheses of basiliolide C and previously unreported epi-basiliolide C are achieved by an Ireland-Claisen/Diels-Alder cascade. The development of a palladium catalyzed cross-coupling of methoxy alkynyl zinc reagents allows for the protecting-group-free syntheses of transtaganolides C and D. Syntheses of transtaganolides C and D are accomplished in a single operation to generate three rings, two all-carbon quaternary centers, and four tertiary stereocenters from a monocyclic, achiral precursor. (Chemical Equation Presented).
Iron-Nickel Dual-Catalysis: A New Engine for Olefin Functionalization and the Formation of Quaternary Centers
Green, Samantha A.,Vásquez-Céspedes, Suhelen,Shenvi, Ryan A.
supporting information, p. 11317 - 11324 (2018/09/18)
Alkene hydroarylation forms carbon-carbon bonds between two foundational building blocks of organic chemistry: olefins and aromatic rings. In the absence of electronic bias or directing groups, only the Friedel-Crafts reaction allows arenes to engage alkenes with Markovnikov selectivity to generate quaternary carbons. However, the intermediacy of carbocations precludes the use of electron-deficient arenes, including Lewis basic heterocycles. Here we report a highly Markovnikov-selective, dual-catalytic olefin hydroarylation that tolerates arenes and heteroarenes of any electronic character. Hydrogen atom transfer controls the formation of branched products and arene halogenation specifies attachment points on the aromatic ring. Mono-, di-, tri-, and tetra-substituted alkenes yield Markovnikov products including quaternary carbons within nonstrained rings.
Rhodium-catalyzed oxygenative addition to terminal alkynes for the synthesis of esters, amides, and carboxylic acids
Kim, Insu,Lee, Chulbom
supporting information, p. 10023 - 10026 (2013/10/01)
A gem of a couple: The title reaction of terminal alkynes with O and Nnucleophiles proceeds in the presence of [Rh(cod)Cl}2], P(4-FC 6H4)3, and 4-picoline N-oxide. Alcohols, amines, and water add to the terminal alkynes to give esters, amides, and carboxylic acids, respectively. The reaction involves formation of a rhodium vinylidene, oxidation to a ketene by oxygen transfer, and nucleophilic addition.
Aspartate-catalyzed asymmetric epoxidation reactions
Peris, Gorka,Jakobsche, Charles E.,Miller, Scott J.
, p. 8710 - 8711 (2008/02/11)
We report enantioselective epoxidation reactions that are catalyzed by aspartic acid-containing peptides. The strategy involves the transient conversion of the aspartate carboxylic acid side chain to the corresponding peracid. Reaction of olefin with the
Asymmetric dihydroxylation of β,γ-unsaturated carboxylic esters with trisubstituted C=C bonds - Enantioselective syntheses of trisubstituted γ-butyrolactones
Kapferer, Tobias,Brueckner, Reinhard
, p. 2119 - 2133 (2007/10/03)
β,γ-Unsaturated esters with stereodefined trisubstitued C=C double bonds were prepared by the Arndt-Eistert homologation of α,β-unsaturated carboxyl halides, by two-step methoxycarbonylation of allylbarium reagents, by deconjugation of α,β-unsaturated esters, and by Horner-Wadsworth-Emmons variants of the Stobbe condensation. Sharpless asymmetric dihydroxylation of the β,γ-unsaturated esters, followed by spontaneous cyclization, afforded β-hydroxy-γ-lactones in moderate to good yields and with enantiomeric excesses of up to 97 %. Similarly, tetrahydroxy-γ-lactones were obtained from diunsaturated esters; these lactones were converted into a bislactone and an unsaturated β-hydroxy γ-lactone. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
Stereo- and regioselectivity of cyclization reactions in conformationally restricted epoxy ketones: Evaluation of C- versus O-alkylation process
Crotti, Paolo,Badalassi, Fabrizio,Di Bussolo, Valeria,Favero, Lucilla,Pineschi, Mauro
, p. 8559 - 8572 (2007/10/03)
The intramolecular addition reaction of metal enolates of ketones to oxiranes has been applied to a series of epoxy ketones derived from cyclohexene oxide. γ-Hydroxy ketones (γ-HKs, C-alkylation products) or hydroxy enol ethers (HEEs, O-alkylation products) are obtained, depending on the nature of the cyclic transition state in each case involved and the application of the Fu?rst-Plattner rule. The formation of HEEs by reaction of the same epoxy ketones under acid conditions is also described. In some cases, regioconvergent or chemoselective processes are conveniently obtained.
Synthesis of γ-lactones and unsaturated bis γ-lactones via Cu-Fe-mediated reductive cyclization of di- and tri-α-halogenated carboxylic esters
Somech, Iris,Shvo, Youval
, p. 153 - 159 (2007/10/03)
A new synthetic route to γ-substituted γ-butyrolactones from alkenes and α-dichloro ester, in the presence of CuCl (catalytic) and Fe(0) (stoichiometric) in acetonitrile, was established. A study of this reaction has demonstrated that the overall process consists of the following reaction steps: (a) addition of the dichloro ester to the olefin via CuCl catalysis; (b) selective reduction of the α-chloro atom in the resulting adduct by Fe(0); (c) cyclization of the resulting γ-chloro ester to γ-butyrolactone. Yields were improved by first carrying out step (a), then steps (b) and (c) in one pot. Selectivity was improved in the presence of a small amount of water. α-Trichloro esters also generated the γ-substituted γ-butyrolactone, albeit in lower yields and selectivity. The latter reaction gave rise to the formation of interesting by-products, namely new unsaturated bis-lactones.
Electroreductive Deoxygenation of Methanesulfonates of α-Hydroxy Esters via a Catalytic Selenation-Deselenation Sequence
Inokuchi, Tsutomu,Sugimoto, Tatsuya,Kusumoto, Masahiko,Torii, Sigeru
, p. 3200 - 3202 (2007/10/02)
The methanesulfonates of α-hydroxy esters were converted to the corresponding deoxygenated esters in 70-88percent yields by the indirect electrolysis with diphenyl diselenide as a recyclable reagent in a divided cell.This deoxygenation method may involve the formation of α-phenylselenoester by replacement of α-methylsulfonyloxy group with phenylselenide anion followed by capture of the α-phenylseleno group with phenylselenide anion.
Solvolytic Hydroperoxide Rearrangements. 2. Oxa Bicyclic Hemiketal Peroxides from Homoallylic and Cyclopropylcarbinyl Precursors
Lillie, Thomas S.,Ronald, Robert C.
, p. 5084 - 5088 (2007/10/02)
Studies in this laboratory have resulted in the discovery of a novel hydrogen peroxide mediated ring expansion that is suitable for the synthesis of medium to large ring oxa bicyclic compounds.This rearrangement involves the solvolysis of homoallylic bros
O-SILYLATED ENOLATES IN ORGANIC SYNTHESIS: SULPHUR-MEDIATED ALKYLATION OF ESTERS WITH ALKENES.
Patel, Shailesh K.,Paterson, Ian
, p. 1315 - 1318 (2007/10/02)
O-Silylated ester enolates can be alkylated, under ZnBr2-catalysis, by the PhSCl-adducts of mono- and di-substituted alkenes to give γ-phenylthioesters, from which sulphur can be removed both reductively and oxidatively.This alkene carbosulphenylation rea
