10342-83-3Relevant articles and documents
Alcohol Oxidations Using Reduced Polyoxovanadates
Campbell, McKenzie L.,Sulejmanovic, Dino,Schiller, Jacqueline B.,Turner, Emily M.,Hwu, Shiou-Jyh,Whitehead, Daniel C.
, (2017)
A full account of our recently communicated room temperature alcohol oxidation using reduced polyoxovanadates (r-POVs) is presented. Extensive optimizations revealed optimal conditions employing 0.02 equiv. of r-POV catalyst Cs5(V14As8O42Cl), 5 equiv. tert-butyl hydrogen peroxide (tBuOOH) as the terminal co-oxidant, in an acetone solvent for the quantitative oxidation of aryl-substituted secondary alcohols to their ketone products. The substrate scope tolerates most aryl substituted secondary alcohols in good to quantitative yields while alkyl secondary and primary activated alcohols were sluggish in comparison under similar conditions. Catalyst recyclability was successful on a 1.0?mmol scale of starting alcohol 1-phenylethanol. The oxidation was also successfully promoted by the VIV/VV mixed valent polyoxovanadate (POV) Cs11Na3Cl5(V15O36Cl). Finally, a third POV, Cs2.64(V5O9)(AsO4)2, was investigated for catalytic activity using our established reaction protocol, but proved ineffective as compared to the other two r-POV catalysts. This study expands the field of POM-mediated alcohol oxidations to include underexplored r-POV catalysts. While our catalysts do not supplant the best catalysts known for the transformation, their study may inform the development of other novel oxidative transformations mediated by r-POVs.
Tethered η5-oxocyclohexadienyl piano-stool ruthenium(II) complexes: A new class of catalysts?
Kechaou-Perrot, Manel,Vendier, Laure,Bastin, Stphanie,Sotiropoulos, Jean-Marc,Miqueu, Karinne,Menndez-Rodrguez, Luca,Crochet, Pascale,Cadierno, Victorio,Igau, Alain
, p. 6294 - 6297 (2014)
The straightforward synthesis of tethered η5-oxocyclohexadienyl Ru(II) complexes is presented. Pioneering results in catalysis show that these original half-sandwich Ru(II) complexes allow the effective isomerization of allylic alcohols under mild conditions without further additives; η5-oxocyclohexadienyl ruthenium complexes may be considered as a new class of catalysts.
One-pot sustainable synthesis of tertiary alcohols by combining ruthenium-catalysed isomerisation of allylic alcohols and chemoselective addition of polar organometallic reagents in deep eutectic solvents
Cicco, Luciana,Rodríguez-álvarez, María J.,Perna, Filippo M.,García-álvarez, Joaquín,Capriati, Vito
, p. 3069 - 3077 (2017)
Ru(iv)-Catalysed redox isomerisation of allylic alcohols has, for the first time, been successfully assembled with the chemoselective addition of organolithium or organomagnesium reagents to the in situ formed ketones, en route to tertiary alcohols, employing deep eutectic solvents as environmentally friendly reaction media. The overall transformation, which formally involves three consecutive and different steps such as (i) the reduction of a C-C double bond, (ii) the oxidation of a secondary carbinol moiety, and (iii) a chemoselective C-C bond formation, takes place in protic and biorenewable eutectic mixtures in a sequential one-pot fashion using a commercially and easily available catalytic system, with excellent conversions (up to 99% yield), at room temperature and under air in the last step, with no concomitant reduction or enolisation processes, and with high atom economy, in agreement with the principles of the so-called green chemistry.
A highly regio- and stereoselective synthesis of ?±-fluorinated imides via fluorination of chiral enamides
Xu, Yan-Shuang,Tang, Yu,Feng, He-Jing,Liu, Ji-Tian,Hsung, Richard P.
, p. 572 - 575 (2015)
A highly ??-facial selective and regioselective fluorination of chiral enamides is described. The reaction involves an enantioselective fluorination exclusively at the electron-rich enamide olefin with N-F reagents such as Selectfluor and N-fluoro-benzenesulfonimide [NFSI] accompanied by trapping of the ?2-fluoro-iminium cationic intermediate with water. The resulting N,O-hemiacetal could be oxidized using Dess-Martin periodinane, leading to an asymmetric sequence for syntheses of chiral ?±-fluoro-imides and optically enriched ?±-fluoro-ketones.
Ruthenium-Catalyzed Redox Isomerizations inside Living Cells
Vidal, Cristian,Tomás-Gamasa, María,Gutiérrez-González, Alejandro,Mascarenas, José L.
, p. 5125 - 5129 (2019)
Tailored ruthenium(IV) complexes can catalyze the isomerization of allylic alcohols into saturated carbonyl derivatives under physiologically relevant conditions, and even inside living mammalian cells. The reaction, which involves ruthenium-hydride intermediates, is bioorthogonal and biocompatible, and can be used for the "in cellulo" generation of fluorescent and bioactive probes. Overall, our research reveals a novel metal-based tool for cellular intervention, and comes to further demonstrate the compatibility of organometallic mechanisms with the complex environment of cells.
Dual oxidation/bromination of alkylbenzenes
Aborways, Marwa M.,Moran, Wesley J.
, p. 983 - 985 (2016)
In the presence of sodium bromide and Oxone, a range of alkylbenzene derivatives are brominated and/or oxidized with up to four C-H bonds being functionalized.
One-Pot Transformation of Ketoximes into Optically Active Alcohols and Amines by Sequential Action of Laccases and Ketoreductases or ω-Transaminases
Correia Cordeiro, Raquel S.,Ríos-Lombardía, Nicolás,Morís, Francisco,Kourist, Robert,González-Sabín, Javier
, p. 1272 - 1277 (2019)
An enzymatic one-pot process for asymmetric transformation of prochiral ketoximes into alcohols or amines was developed by sequential coupling of a laccase-catalyzed deoximation either with a ketone reduction (ketoreductase, KRED) or bioamination (ω-transaminase, ω-TA) in aqueous medium. An accurate selection of biocatalysts provided the corresponding products in excellent enantiomeric excesses and overall conversions ranging from 83 to >99 % for alcohols and 70 to >99 % for amines. Likewise, the employment of exclusively 1 % (w/w) of Cremophor, a polyethoxylated castor oil, as co-solvent enabled to reach concentrations up to 100 mM in the chiral alcohols cascade.
Isomerization of Allylic Alcohols to Ketones Catalyzed by Well-Defined Iron PNP Pincer Catalysts
Xia, Tian,Wei, Zhihong,Spiegelberg, Brian,Jiao, Haijun,Hinze, Sandra,de Vries, Johannes G.
, p. 4043 - 4049 (2018)
[Fe(PNP)(CO)HCl] (PNP=di-(2-diisopropylphosphanyl-ethyl)amine), activated in situ with KOtBu, is a highly active catalyst for the isomerization of allylic alcohols to ketones without an external hydrogen supply. High reaction rates were obtained at 80 °C, but the catalyst is also sufficiently active at room temperature with most substrates. The reaction follows a self-hydrogen-borrowing mechanism, as verified by DFT calculations. An alternative isomerization through alkene insertion and β-hydride elimination could be excluded on the basis of a much higher barrier. In alcoholic solvents, the ketone product is further reduced to the saturated alcohol.
Highly water-soluble arene-ruthenium(ii) complexes: Application to catalytic isomerization of allylic alcohols in aqueous medium
Lastra-Barreira, Beatriz,Diez, Josefina,Crochet, Pascale
, p. 1681 - 1686 (2009)
Arene-ruthenium(ii) derivatives [RuCl2(η6-C 6H5OCH2CH2OH)(L)] (L = P(OMe) 3 (2a), P(OEt)3 (2b), P(OiPr)3 (2c), P(OPh)3 (2d), PPh3 (2e)) have been prepared from the dimer [{RuCl(μ-Cl)(η6-C6H5OCH 2CH2OH)}2] and the appropriate P-donor ligand. The hydroxyethoxy substituent on the arene induces water-solubility of the resulting complexes (up to 755 g L-1); in particular derivative 2a being one hundred times more soluble in water than its p-cymene congener [RuCl2(η6-p-cymene){P(OMe)3}]. Compounds 2a-e are active catalysts for isomerization of allylic alcohols into the corresponding ketones in aqueous medium. The best performances are obtained with derivatives 2a-c which have shown the highest activity reported to date for the isomerization of aromatic or disubstituted substrates in water. The Royal Society of Chemistry 2009.
Programming cascade reactions interfacing biocatalysis with transition-metal catalysis in: Deep Eutectic Solvents as biorenewable reaction media
Cicco, Luciana,Ríos-Lombardía, Nicolás,Rodríguez-álvarez, María J.,Morís, Francisco,Perna, Filippo M.,Capriati, Vito,García-álvarez, Joaquín,González-Sabín, Javier
, p. 3468 - 3475 (2018)
The first application of Deep Eutectic Solvents (DESs) in the asymmetric bioreduction of ketones has been accomplished for purified ketoreductases (KREDs). The performance of the biocatalysts was enhanced by increasing the percentage of neoteric solvent in DES-buffer mixtures. At a buffer content of 50% (w/w) and even 20% (w/w), the combination of either choline chloride (ChCl)/glycerol (Gly) (1:2) or ChCl/sorbitol (1:1) proved to be most effective for achieving up to >99% conversion and up to >99% enantiomeric excess of the corresponding secondary alcohols. Moreover, this reaction medium was used to perform the first example of a chemoenzymatic cascade process in DES-buffer mixtures, namely the ruthenium-catalysed isomerisation of racemic allylic alcohols coupled with a further enantioselective bioreduction, in both sequential and concurrent modes.
