121054-03-3Relevant articles and documents
Alkali salt of L-proline as an efficient and practical catalyst for the cyanosilylation of a wide variety of carbonyl compounds under solvent-free conditions
Shen, Zhi-Liang,Ji, Shun-Jun
, p. 775 - 791 (2009)
The alkali salt of L-proline was demonstrated to be an efficient and practical catalyst for the cyanosilylation of a wide variety of simple and functionalized carbonyl compounds under solvent-free conditions. The reactions proceeded smoothly at room temperature to afford the corresponding cyanohydrins in good to excellent yields. Copyright Taylor & Francis Group, LLC.
Ionic liquid [omim][PF6] as an efficient and recyclable reaction media for the cyanosilylation of aldehydes without Lewis acid or any special activation
Shen, Zhi-Liang,Ji, Shun-Jun,Loh, Teck-Peng
, p. 3137 - 3139 (2005)
Ionic liquid [omim][PF6] has been demonstrated as an efficient and environmentally friendly reaction media as well as a promoter for the cyanosilylation of aldehydes under mild conditions. In addition, the recovered ionic liquid could be reused for subsequent runs with only a gradual decrease in activity.
Nickel-Catalyzed, Reductive C(sp3)?Si Cross-Coupling of α-Cyano Alkyl Electrophiles and Chlorosilanes
Oestreich, Martin,Zhang, Liangliang
supporting information, p. 18587 - 18590 (2021/07/25)
A nickel/zinc-catalyzed cross-electrophile coupling of alkyl electrophiles activated by an α-cyano group and chlorosilanes is reported. Elemental zinc is the stoichiometric reductant in this reductive coupling process. By this, a C(sp3)?Si bond can be formed starting from two electrophilic reactants whereas previous methods rely on the combination of carbon nucleophiles and silicon electrophiles or vice versa.
CO2-Enabled Cyanohydrin Synthesis and Facile Iterative Homologation Reactions**
Juhl, Martin,Petersen, Allan R.,Lee, Ji-Woong
supporting information, p. 228 - 232 (2020/11/30)
Thermodynamic and kinetic control of a chemical process is the key to access desired products and states. Changes are made when a desired product is not accessible; one may manipulate the reaction with additional reagents, catalysts and/or protecting groups. Here we report the use of carbon dioxide to accelerate cyanohydrin synthesis under neutral conditions with an insoluble cyanide source (KCN) without generating toxic HCN. Under inert atmosphere, the reaction is essentially not operative due to the unfavored equilibrium. The utility of CO2-mediated selective cyanohydrin synthesis was further showcased by broadening Kiliani–Fischer synthesis under neutral conditions. This protocol offers an easy access to a variety of polyols, cyanohydrins, linear alkylnitriles, by simply starting from alkyl- and arylaldehydes, KCN and an atmospheric pressure of CO2.
CO2-Mediated Non-Destructive Cyanide Wastewater Treatment
Juhl, Martin,Lee, Ji-Woong,Petersen, Allan R.,Petrovic, Aleksa
supporting information, p. 5003 - 5007 (2021/09/30)
The facile removal of cyanide anions from cyanide-containing water was achieved using CO2 in conjunction with aldehydes which can be recycled from the process. The conversion of the cyanide ion into an insoluble cyanohydrin in water allowed the removal of cyanide and could be used as a method for treating cyanide contaminated wastewater and for recovering cyanide or cyanohydrins for further applications.
Access to β-Ketonitriles through Nickel-Catalyzed Carbonylative Coupling of α-Bromonitriles with Alkylzinc Reagents
Donslund, Aske S.,Neumann, Karoline T.,Corneliussen, Nicklas P.,Grove, Ebbe K.,Herbstritt, Domenique,Daasbjerg, Kim,Skrydstrup, Troels
supporting information, p. 9856 - 9860 (2019/07/09)
Herein, we report a nickel-catalyzed carbonylative coupling of α-bromonitriles and alkylzinc reagents with near stoichiometric carbon monoxide to give β-ketonitriles in good yields. The reaction is catalyzed by a readily available and stable nickel(II) pincer complex. The developed protocol tolerates substrates bearing a variety of functional groups, which would be problematic or incompatible with previous synthetic methods. Additionally, we demonstrate the suitability of the method for carbon isotope labeling by the synthesis of 13C-labeled β-ketonitriles and their transformation into isotopically labeled heterocycles.
Hydroxynitrile Lyase Isozymes from Prunus communis: Identification, Characterization and Synthetic Applications
Zheng, Yu-Cong,Xu, Jian-He,Wang, Hui,Lin, Guo-Qiang,Hong, Ran,Yu, Hui-Lei
, p. 1185 - 1193 (2017/04/13)
Biocatalysts originating from Badamu (Prunus communis) have been applied to catalyze the asymmetric synthesis of (R)-4-methylsulfanylmandelonitrile, a key building block of thiamphenicol and florfenicol. Here, four hydroxynitrile lyase (HNL) isozymes from Badamu were cloned and heterologously expressed in Pichia pastoris. The biochemical properties and catalytic performances of these isozymes were comprehensively explored to evaluate their efficiency and selectivity in asymmetric synthesis. Among then, PcHNL5 was identified with outstanding activity and enantioselectivity in asymmetric hydrocyanation. Under the optimized mild biphasic reaction conditions, seventeen prochiral aromatic aldehydes were converted to valuable chiral cyanohydrins with good yields (up to 94%) and excellent optical purities (up to >99.9% ee), which provide a facile access to numerous chiral amino alcohols, hypoglycemic agents, angiotension converting enzyme (ACE) inhibitors and β-blockers. This work therefore underlines the importance of discovering the most potent biocatalyst among a group of isozymes for converting unnatural substrates into value-added products. (Figure presented.).
Copper-Catalyzed Substitution of α-Triflyloxy Nitriles and Esters with Silicon Nucleophiles under Inversion of the Configuration
Scharfbier, Jonas,Hazrati, Hamideh,Irran, Elisabeth,Oestreich, Martin
supporting information, p. 6562 - 6565 (2017/12/26)
A copper-catalyzed nucleophilic displacement of α-triflyloxy nitriles and esters with silicon nucleophiles allows for the stereospecific generation of highly enantioenriched α-silylated carboxyl compounds. The enantioselective synthesis of α-silylated nitriles is unprecedented. The catalytic system exhibits good functional group tolerance. The stereochemical course of the substitution is shown to proceed with inversion of the configuration. The new reaction is an addition to the still limited number of methods for catalytic C(sp3)-Si cross-coupling.
Metallation–substitution of an α-oxygenated chiral nitrile
Alshawish, Madeha R.,Barker, Graeme,Measom, Nicholas D.,Coldham, Iain
, p. 601 - 608 (2017/05/24)
Deprotonation of a chiral alpha-oxygenated nitrile with the base 2,2,6,6-tetramethylpiperidylmagnesium chloride, TMPMgCl, gives rise to a chiral magnesiated nitrile, and this anion has sufficient configurational stability at low temperature to allow the formation of highly enantiomerically enriched substituted nitrile products after electrophilic quench.
Nickel-Catalyzed Asymmetric Reductive Cross-Coupling between Heteroaryl Iodides and α-Chloronitriles
Kadunce, Nathaniel T.,Reisman, Sarah E.
, p. 10480 - 10483 (2015/09/28)
A Ni-catalyzed asymmetric reductive cross-coupling of heteroaryl iodides and α-chloronitriles has been developed. This method furnishes enantioenriched α,α-disubstituted nitriles from simple organohalide building blocks. The reaction tolerates a variety of heterocyclic coupling partners, including pyridines, pyrimidines, quinolines, thiophenes, and piperidines. The reaction proceeds under mild conditions at room temperature and precludes the need to pregenerate organometallic nucleophiles.
