16635-54-4Relevant articles and documents
Binuclear complexes for aerobic oxidation of primary alcohols and carbohydrates
Striegler, Susanne,Dunaway, Natasha A.,Gichinga, Moses G.,Milton, Lisa K.
, p. 7927 - 7932 (2010)
The influence of electron-donating and electron-accepting properties of three pentadentate ligands was determined in connection with the aerobic oxidation ability of the corresponding binuclear copper(II) complexes for benzyl and allyl alcohols; additionally, the catalytic performance of their palladium and platinum analogs was characterized under comparable conditions. Quantitative aerobic oxidation of benzyl alcohol at 40 °C was achieved with a binuclear copper(II) complex - TEMPO catalyst in 2.5 h, while the regioselective aerobic oxidation of underivatized methyl-β-d-glucopyranoside was accomplished in about 35% yield at 60 °C after 24 h.
Synthesis of regioselectively deuterated cyclopropanes
Duffault, Jean-Marc,Hanoteau, Pascal,Parrilla, Alfredo,Einhorn, Jacques
, p. 3257 - 3265 (1996)
A regioselective synthesis of deuterated aliphatic cyclopropanes has been developed to furnish labeled substrates for gas-phase ion-molecule reaction studies.
Palladium-Catalyzed Enantioselective Redox-Relay Heck Alkynylation of Alkenols To Access Propargylic Stereocenters
Chen, Zhi-Min,Nervig, Christine S.,DeLuca, Ryan J.,Sigman, Matthew S.
supporting information, p. 6651 - 6654 (2017/05/29)
An enantioselective redox-relay Heck alkynylation of di- and trisubstituted alkenols to construct propargylic stereocenters is disclosed using a new pyridine oxazoline ligand. This strategy allows direct access to chiral β-alkynyl carbonyl compounds employing allylic alcohol substrates in contrast to more traditional conjugate addition methods.
Method for preparing Z-isomer by E-isomer of alpha, beta-nonsaturated carbonyl compound
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Paragraph 0054; 0055, (2017/04/29)
The invention provides a method for preparing a Z-isomer by an E-isomer of an alpha, beta-nonsaturated carbonyl compound. The method uses nitrogen-containing chiral binaphthol phosphoramidite to prepare a catalyst, under mild reaction condition, the E-isomer of the alpha, beta-nonsaturated carbonyl compound is efficiently conversed to the Z-isomer. The method is especially suitable for preparing neral through isomerization of partial geranial in a citral split residual material, the citral with mol ratio of the obtained geranial to neral being 1:1 can be reused for splitting the neral, raw material utilization rate is increased, and the cost is reduced.
Characterization of the monolignol oxidoreductase AtBBE-like protein 15 L182V for biocatalytic applications
Pils, Sabine,Schnabl, Kordula,Wallner, Silvia,Daniel, Bastian,Macheroux, Peter,Kljajic, Marko,Kupresanin, Nina,Breinbauer, Rolf,Fuchs, Michael,Rocha, Raquel,Schrittwieser, Joerg H.,Kroutil, Wolfgang
, p. S6 - S14 (2018/04/05)
Monolignol oxidoreductases from the berberine bridge enzyme-like (BBE-like) protein family (pfam 08031) catalyze the oxidation of monolignols to the corresponding aldehydes. In this report, we explore the potential of a monolignol oxidoreductase from Arabidopsis thaliana (AtBBE-like protein 15) as biocatalyst for oxidative reactions. For this study we employed a variant with enhanced reactivity towards oxygen, which was obtained by a single amino acid exchange (L182V). The pH and temperature optima of the purified AtBBE-like protein 15 L182V were determined as well as the tolerance toward organic co-solvents; furthermore the substrate scope was characterized. The enzyme has a temperature optimum of 50 °C and retains more than 50% activity between pH 5 and pH 10 within 5 min. The enzyme shows increased activity in the presence of various co-solvents (10–50% v/v), including acetonitrile, 2-propanol, 1,4-dioxane, and dimethyl sulfoxide. Primary benzylic and primary or secondary allylic alcohols were accepted as substrates. The enantioselectivity E in the oxidation of secondary alcohols was good to excellent (E>34 to?>200).
Copper(I)/ABNO-catalyzed aerobic alcohol oxidation: Alleviating steric and electronic constraints of Cu/TEMPO catalyst systems
Steves, Janelle E.,Stahl, Shannon S.
supporting information, p. 15742 - 15745 (2013/11/06)
Cu/TEMPO catalyst systems promote efficient aerobic oxidation of sterically unhindered primary alcohols and electronically activated substrates, but they show reduced reactivity with aliphatic and secondary alcohols. Here, we report a catalyst system, consisting of (MeObpy)CuI(OTf) and ABNO (MeObpy =4,4′-dimethoxy-2,2′-bipyridine; ABNO = 9-azabicyclo[3.3.1]nonane N-oxyl), that mediates aerobic oxidation of all classes of alcohols, including primary and secondary allylic, benzylic, and aliphatic alcohols with nearly equal efficiency. The catalyst exhibits broad functional group compatibility, and most reactions are complete within 1 h at room temperature using ambient air as the source of oxidant.
Highly practical copper(I)/TEMPO catalyst system for chemoselective aerobic oxidation of primary alcohols
Hoover, Jessica M.,Stahl, Shannon S.
supporting information; experimental part, p. 16901 - 16910 (2011/12/04)
Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O2 as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)CuI/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic, and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups.
Copper on boehmite: A simple, selective, efficient and reusable heterogeneous catalyst for oxidation of alcohols with periodic acid in water at room temperature
Babu, S. Ganesh,Priyadarsini, P. Aruna,Karvembu
experimental part, p. 218 - 224 (2011/11/05)
Oxidation of various aliphatic, aromatic, alicyclic, benzylic and allylic alcohols to corresponding carbonyl compounds is studied in water at room temperature over copper on boehmite [Cu/AlO(OH)] catalyst which is prepared from CuCl2·2H2O, pluronic P123 and Al(O-sec-Bu) 3. The prepared catalyst was characterized by HR-TEM, SEM-EDX and IR spectroscopy. The reaction conditions for catalytic oxidation of alcohols are optimized with different mole ratio, solvents, and oxidants using 1-phenylethanol system as a model. The scope of the reaction is extended to various types of alcohols. Chemoselectivity, heterogeneity and reusability tests were performed. The use of water as a solvent at room temperature makes the reaction interesting from both an economic and environmental point of view.
Biooxidation of Primary Alcohols to Aldehydes through Hydrogen Transfer Employing Janibacter terrae
Orbegozo, Thomas,De Vries, Johannes G.,Kroutil, Wolfgang
experimental part, p. 3445 - 3448 (2010/09/05)
Chemoselective oxidations still represent a challenge for chemists. Lyophilized cells of Janibacter terrae were employed for the chemoselective oxidation of primary alcohols to the corresponding aldehydes by hydrogen transfer with the use of acetaldehyde as the hydrogen acceptor. Secondary alcohol moieties were transformed at a much slower rate. The substrate spectrum encompasses substituted benzyl alcohols, whereby substrates with a substituent in the meta position were well tolerated, whereas only very small substituants were tolerated in the ortho position. Furthermore, nalkanols and allylic alcohols were transformed with good conversions. The biocatalyst was compatible with DMSO as a water miscible organic solvent up to 30 % v/v.
Oxidation of allylic alcohols to α,β-unsaturated carbonyl compounds with aqueous hydrogen peroxide under organic solvent-free conditions
Kon, Yoshihiro,Usui, Yoko,Sato, Kazuhiko
, p. 4399 - 4400 (2008/04/01)
Allylic alcohols are chemoselectively oxidized to α,β- unsaturated carbonyl compounds in high yield with aqueous H2O 2 in the presence of Pt black catalyst under organic solvent-free conditions. The catalyst is easily recyclable and effective for at least 7 cycles. The Royal Society of Chemistry.
