24506-17-0Relevant articles and documents
Synthesis of β-hydroxyamides through ruthenium-catalyzed hydration/transfer hydrogenation of β-ketonitriles in water: Scope and limitations
González-Fernández, Rebeca,Crochet, Pascale,Cadierno, Victorio
, p. 90 - 101 (2019/06/18)
A cascade process for the straightforward one-pot conversion of β-ketonitriles into β-hydroxyamides is presented. The process, that proceeds in water employing the arene-ruthenium(II) complex [RuCl2(η6-p-cymene){P(4-C6H4F)2Cl}] as catalyst in combination with sodium formate, involves the initial hydration of the β-ketonitrile substrates to generate the corresponding β-ketoamide intermediates, which subsequently undergo the transfer hydrogenation (TH) of the carbonyl group. Employing a family of forty different β-ketonitriles, featuring diverse substitution patterns, the scope and limitations of the process have been established.
Strengthening the Combination between Enzymes and Metals in Aqueous Medium: Concurrent Ruthenium-Catalyzed Nitrile Hydration - Asymmetric Ketone Bioreduction
Liardo, Elisa,González-Fernández, Rebeca,Ríos-Lombardía, Nicolás,Morís, Francisco,García-álvarez, Joaquín,Cadierno, Victorio,Crochet, Pascale,Rebolledo, Francisca,González-Sabín, Javier
, p. 4676 - 4682 (2018/09/25)
A dual ruthenium/ketoreductase catalytic system has been developed for the conversion of β-ketonitriles into optically active β-hydroxyamides through an unprecedented hydration/bioreduction cascade process in aqueous medium working in concurrent mode. The ketoreductase-mediated ketone reduction took place with exquisite stereoselectivity and it was simultaneous to the nitrile hydration promoted by the ruthenium catalyst. The overall transformation occurred: (i) employing commercially and readily available catalytic systems (ii) under mild reaction conditions, (iii) with high degree of conversion and excellent stereoselectivity, and (iv) without the need to isolate intermediates and with high final product yields. This genuine process demonstrates the benefits of combining metal and enzymatic catalysis to tackle the limitations arising from each field.
Synthesis of α-alkenyl-β-hydroxy adducts by α-addition of unprotected 4-bromocrotonic acid and amides with aldehydes and ketones by chromium(II)-mediated reactions
Wessjohann, Ludger A.,Wild, Harry,Ferreira, Leonildo A.,Schrekker, Henri S.
, p. 674 - 679 (2016/07/19)
The regioselective and diastereoselective chromium(II)-mediated reactions of 4-bromocrotonic acid or amides with aldehydes and ketones can proceed without the need to protect protic sites to generate the respective α-alkenyl-β-hydroxy adducts, i.e. formally the addition of the α-anion of a carboxylic acid or amide to an oxo-compound is featured.
Ruthenium-Catalyzed Synthesis of β-Hydroxyamides from β-Ketonitriles in Water
González-Fernández, Rebeca,Crochet, Pascale,Cadierno, Victorio
supporting information, p. 6164 - 6167 (2016/12/09)
An unprecedented hydration/transfer hydrogenation tandem process for the catalytic conversion of β-ketonitriles into synthetically useful β-hydroxyamides in water has been developed, making use of the ruthenium(II) complex [RuCl2(η6-
Hydration of nitriles to amides by a chitin-supported ruthenium catalyst
Matsuoka, Aki,Isogawa, Takahiro,Morioka, Yuna,Knappett, Benjamin R.,Wheatley, Andrew E. H.,Saito, Susumu,Naka, Hiroshi
, p. 12152 - 12160 (2015/02/19)
Chitin-supported ruthenium (Ru/chitin) promotes the hydration of nitriles to carboxamides under aqueous conditions. The nitrile hydration can be performed on a gram-scale and is compatible with the presence of various functional groups including olefins, aldehydes, carboxylic esters and nitro and benzyloxycarbonyl groups. The Ru/chitin catalyst is easily prepared from commercially available chitin, ruthenium(III) chloride and sodium borohydride. Analysis of Ru/chitin by high-resolution transmission electron microscopy indicates the presence of ruthenium nanoparticles on the chitin support.
Heterogeneous versus homogeneous copper(II) catalysis in enantioselective conjugate-addition reactions of boron in water
Kitanosono, Taku,Xu, Pengyu,Kobayashi, Shu
supporting information, p. 179 - 188 (2014/01/06)
We have developed CuII-catalyzed enantioselective conjugate-addition reactions of boron to α,β-unsaturated carbonyl compounds and α,β,γ,δ-unsaturated carbonyl compounds in water. In contrast to the previously reported CuI catalysis that required organic solvents, chiral CuII catalysis was found to proceed efficiently in water. Three catalyst systems have been exploited: cat. 1: Cu(OH)2 with chiral ligand L1; cat. 2: Cu(OH)2 and acetic acid with ligand L1; and cat. 3: Cu(OAc)2 with ligand L1. Whereas cat. 1 is a heterogeneous system, cat. 2 and cat. 3 are homogeneous systems. We tested 27 α,β-unsaturated carbonyl compounds and an α,β-unsaturated nitrile compound, including acyclic and cyclic α,β-unsaturated ketones, acyclic and cyclic β,β- disubstituted enones, acyclic and cyclic α,β-unsaturated esters (including their β,β-disubstituted forms), and acyclic α,β-unsaturated amides (including their β,β-disubstituted forms). We found that cat. 2 and cat. 3 showed high yields and enantioselectivities for almost all substrates. Notably, no catalysts that can tolerate all of these substrates with high yields and high enantioselectivities have been reported for the conjugate addition of boron. Heterogeneous cat. 1 also gave high yields and enantioselectivities with some substrates and also gave the highest TOF (43 200 h-1) for an asymmetric conjugate-addition reaction of boron. In addition, the catalyst systems were also applicable to the conjugate addition of boron to α,β,γ, δ-unsaturated carbonyl compounds, although such reactions have previously been very limited in the literature, even in organic solvents. 1,4-Addition products were obtained in high yields and enantioselectivities in the reactions of acyclic α,β,γ,δ-unsaturated carbonyl compounds with diboron 2 by using cat. 1, cat. 2, or cat. 3. On the other hand, in the reactions of cyclic α,β,γ,δ-unsaturated carbonyl compounds with compound 2, whereas 1,4-addition products were exclusively obtained by using cat. 2 or cat. 3, 1,6-addition products were exclusively produced by using cat. 1. Similar unique reactivities and selectivities were also shown in the reactions of cyclic trienones. Finally, the reaction mechanisms of these unique conjugate-addition reactions in water were investigated and we propose stereochemical models that are supported by X-ray crystallography and MS (ESI) analysis. Although the role of water has not been completely revealed, water is expected to be effective in the activation of a borylcopper(II) intermediate and a protonation event subsequent to the nucleophilic addition step, thereby leading to overwhelmingly high catalytic turnover. Copyright
A high throughput screening strategy for the assessment of nitrile-hydrolyzing activity towards the production of enantiopure β-hydroxy acids
Coady, Tracey M.,Coffey, Lee V.,O'Reilly, Catherine,Owens, Erica B.,Lennon, Claire M.
, p. 150 - 155 (2013/10/01)
Nitrile hydrolysing enzymes have found wide use in the pharmaceutical industry for the production of fine chemicals. This work presents a strategy that facilitates the rapid identification of bacterial isolates demonstrating nitrile hydrolysing activity. The strategy incorporates toxicity, starvation and induction studies along with subsequent colorimetric screening for activity, further focusing the assessment towards the substrates of interest. This high-throughput strategy uses a 96 well plate system, and has enabled the rapid biocatalytic screening of 256 novel bacterial isolates towards β-hydroxynitriles. Results demonstrate the strategy's potential to rapidly assess a variety of β-hydroxynitriles including aliphatic, aromatic and dinitriles. A whole cell catalyst Rhodococcus erythropolis SET1 was identified and found to catalyse the hydrolysis of 3-hydroxybutyronitrile with remarkably high enantioselectivity under mild conditions, to afford (S)-3-hydroxybutyric acid in 42% yield and >99.9% ee. The biocatalytic capability of this strain including the variation of parameters such as temperature and time were further investigated and all results indicate the presence of a highly enantioselective if not enantiospecific nitrilase enzyme within the microbial whole cell.
One-pot nitrile aldolization/hydration operation giving β-hydroxy carboxamides
Goto, Akihiro,Naka, Hiroshi,Noyori, Ryoji,Saito, Susumu
supporting information; experimental part, p. 1740 - 1743 (2011/12/16)
Rhodium to the rescue: The formal aldol products of carboxamides (CONH 2) were obtained by using a RhI(OR) (R=H, Me) catalyst under essentially neutral pH and ambient conditions. This novel aldol strategy is based on the catalytic al
A new facile chemoenzymatic synthesis of levamisole
Kamal, Ahmed,Khanna, G.B. Ramesh,Krishnaji,Ramu
, p. 613 - 615 (2007/10/03)
An efficient and facile chemoenzymatic synthesis of levamisole by employing lipase-mediated resolution of 3-hydroxy-3-phenylpropanenitrile followed by its conversion to β-amino alcohol as the key intermediate is described.
Enantioselective reduction of β-keto amides by the fungus Mortierella isabellina
Quiros, Margarita,Rebolledo, Francisca,Liz, Ramon,Gotor, Vicente
, p. 3035 - 3038 (2007/10/03)
Incubations of the fungus Mortierella isabellina NRRL 1757 with 3-oxo-3-phenylpropanamide, 3-oxobutanamide and with some of their N-alkyl derivatives afford the corresponding (S)-3-hydroxyamides usually in high chemical yields and enantiomeric excesses.
