58289-69-3Relevant academic research and scientific papers
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.
Synthesis of Acrylonitriles via Mild Base Promoted Tandem Nucleophilic Substitution-Isomerization of α-Cyanohydrin Methanesulfonates
Liu, Shiwen,Meng, Lingling,Zeng, Xiaojun,Hammond, Gerald B.,Xu, Bo
supporting information, p. 913 - 917 (2021/04/05)
Main observation and conclusion: We have developed an efficient synthesis of acrylonitriles via mild base promoted tandem nucleophilic substitution-isomerization of α-cyanohydrin methanesulfonates with alkenylboronic acids. This transition metal-free protocol works under simple and mild conditions and offers good chemical yields for a wide range of substrates and demonstrates good functional group tolerance. (Figure presented.).
Highly chemoselective and efficient Strecker reaction of aldehydes with TMSCN catalyzed by MgI2 etherate under solvent-free conditions
He, Kailun,Liu, Huijun,Zhang, Xingxian,Zhou, Jing
supporting information, p. 933 - 936 (2019/03/08)
Strecker reaction of various substituted aromatic aldehydes, heteroaromatic aldehydes, aliphatic aldehydes and α,β-unsaturated aldehydes with trimethylsilyl cyanide (TMSCN) was realized in the presence of 5 mol % of MgI2 etherate in a mild, efficient and highly chemoselective manner under solvent-free conditions.
Acceptorless and Base-free Dehydrogenation of Cyanohydrin with (η6-Arene)halide(Bidentate Phosphine)ruthenium(II) Complex
Kim, Kicheol,Moeljadi, Adhitya Mangala Putra,Hirao, Hajime,Hong, Soon Hyeok
supporting information, p. 3292 - 3298 (2017/09/06)
Ruthenium-catalyzed dehydrogenation of cyanohydrins under acceptorless and base-free conditions was demonstrated for the first time in the synthesis of acyl cyanide. As opposed to the thermodynamically preferred elimination of hydrogen cyanide, the dehydrogenation of cyanohydrins could be kinetically controlled with ruthenium (II) bidentate phosphine complexes. The effects of the arene, phosphine ligands and counter anions were investigated in regard to catalytic activity and selectivity. Selective dehydrogenation can occur via β-hydride elimination with the experimentally observed [(alkoxide)Ru] complex. (Figure presented.).
An orthogonal biocatalytic approach for the safe generation and use of HCN in a multistep continuous preparation of chiral O-acetylcyanohydrins
Brahma, Aischarya,Musio, Biagia,Ismayilova, Uliviya,Nikbin, Nikzad,Kamptmann, Sonja B.,Siegert, Petra,Jeromin, Günter E.,Ley, Steven V.,Pohl, Martina
supporting information, p. 262 - 266 (2016/01/20)
An enantioselective preparation of O-acetylcyanohydrins has been accomplished by a three-step telescoped continuous process. The modular components enabled an accurate control of two sequential biotransformations, safe handling of an in situ generated hazardous gas, and in-line stabilization of products. This method proved to be advantageous over the batch protocols in terms of reaction time (40 min vs 345 min) and ease of operation, opening up access to reactions which have often been neglected due to safety concerns.
P(NMe2)3-Mediated Umpolung Alkylation and Nonylidic Olefination of α-Keto Esters
Wang, Sunewang Rixin,Radosevich, Alexander T.
supporting information, p. 3810 - 3813 (2015/08/18)
A commercial phosphorus-based reagent (P(NMe2)3) mediates umpolung alkylation of methyl aroylformates with benzylic and allylic bromides, leading to either Barbier-type addition or ylide-free olefination products upon workup. The reaction sequence is initiated by a two-electron redox addition of the tricoordinate phosphorus reagent with an α-keto ester compound (Kukhtin-Ramirez addition). A mechanistic rationale is offered for the chemoselectivity upon which the success of this nonmetal mediated C-C bond forming strategy is based.
Solid phase behavior in the chiral systems of various 2-hydroxy-2-phenylacetic acid (mandelic acid) derivatives
Von Langermann, Jan,Temmel, Erik,Seidel-Morgenstern, Andreas,Lorenz, Heike
, p. 721 - 728 (2015/03/30)
The solid phase behavior of a series of monosubstituted F-, Cl-, Br-, I-, and CH3- and two 2,4-halogen-disubstituted 2-hydroxy-2-phenylacetic acid (mandelic acid) derivatives was investigated. The study includes detailed information about melting temperature, melting enthalpy, X-ray diffraction data, as well as selected binary phase diagrams of the respective chiral systems. Aside from the known metastable conglomerate 2-chloromandelic acid, evidence for two more metastable conglomerates was found.
A magnetic nanoparticle catalyzed eco-friendly synthesis of cyanohydrins in a deep eutectic solvent
Azizi, Najmedin,Rahimi, Zahra,Alipour, Masoumeh
, p. 61191 - 61198 (2015/07/28)
Magnetic Fe3O4 nanoparticles in deep eutectic solvents (DESs) have been regard as excellent catalysts for highly efficient cyanosilylation of various aldehydes and epoxides using trimethylsilyl cyanide TMSCN in high yields with excellent selectivity. Fe3O4 nanoparticles were synthesized and applied as a catalyst for the preparation of a wide variety of cyanohydrins (α-hydroxy nitriles and β-hydroxy nitriles) in readily available urea-choline chloride deep eutectic solvent DES as the most promising environmentally benign and cost-effective green solvent. Magnetic DES operates at very mild reaction conditions and can be easily recycled without significant loss of its catalytic activity.
Relationships between the racemic structures of substituted mandelic acids containing 8- and 10-membered hydrogen bonded dimer rings
Coles,Ellis,Leung,Sarson,Threlfall,Tizzard
, p. 10816 - 10823 (2015/02/19)
The structures of 27 monosubstituted mandelic acids, including several of their polymorphs, plus unsubstituted mandelic acid itself (two polymorphs) are investigated for structural similarity. The results, presented pictorially as a structural relationship plot, show that rather more structures are built up from the carboxyl-chain hydroxyl hydrogen bonded dimer than from the conventional carboxylic acid dimer. The results show how all the structures are related and, based on the two types of dimer, the degree of similarity that they possess. Some structures with Z′ > 1 contain both sorts of dimers and there are many examples of isostructural sets within the structures so far determined. We also present an example where analysing similarity in related families of structures highlights a structure that should be present and which has indeed then proceeded to be synthesised and determined.
NaCN/DOWEX(R)50WX4: A convenient system for synthesis of cyanohydrins from aldehydes
Sofighaderi, Sargol,Setamdideh, Davood
, p. 1135 - 1137 (2014/03/21)
A variety of cyanohydrins were prepared from Aldehydes with sodium cyanide and DOWEX(R)50WX4 in a convenient procedure.
