13312-84-0Relevant 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.
Design and synthesis of a novel series of cyanoindole derivatives as potent γ-secretase modulators
Bischoff, Fran?ois P.,Velter, Adriana Ingrid,Minne, Garrett,Pieters, Serge,Berthelot, Didier,De Cleyn, Michel,Gijsen, Harrie J.M.,Macdonald, Gregor,Surkyn, Michel,Van Brandt, Sven,Van Roosbroeck, Yves,Zavattaro, Chiara,Mercken, Marc,Austin, Nigel,Dhuyvetter, Deborah,Borghys, Herman,Ahmad, Ishtiyaque,Samanta, Swapan Kumar
, p. 1737 - 1745 (2019/05/22)
The discovery, design and synthesis of a new series of GSMs is described. The classical imidazole heterocycle has been replaced by a cyano group attached to an indole nucleus. The exploration of this series has led to compound 26-S which combined high in
Refining method of high-purity O-chloromandelonitrile
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Paragraph 0022; 0023, (2019/10/01)
The invention provides a refining method of high-purity o-chloromandelonitrile. The refining method comprises: (a) carrying out pressure reducing distillation on an o-chloromandelonitrile mother liquor to obtain a concentrated liquid; (b) adding the concentrated liquid obtained in the step (a) into an alkane-based solvent to obtain a mixed solution; and (c) cooling the mixed solution obtained in the step (b) to a temperature of 0-10 DEG C, crystallizing, carrying out suction filtration, and drying to obtain o-chloromandelonitrile. According to the present invention, the method has characteristics of simple operation, high product purity and high yield.
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.
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.).
Preparation and reactions of certain racemic and optically active cyanohydrins derived from 2-chlorobenzaldehyde, 4-fluorobenzaldehyde, benzo[d][1,3]-dioxole-5-carbaldehyde and 2,3-dihydrobenzo[b][1,4]dioxine-6-carbaldehyde. Antimicrobial and in vitro antitumor evaluation of the products
Yosef, Hisham Abdallah A.,Elmasry,Ibrahim, Nabila M.,Ismael, Eman H. I.,Mahran
, p. 301 - 328 (2017/06/08)
THE CHEMOENZYMATIC reaction of selected aldehydes, namely 2-chlorobenzaldehyde (1a), 4-fluorobenzaldehyde (1b), benzo[d][1,3]dioxole-5-carbaldehyde (1c) and/or 2,3-dihydrobenzo [b] [1,4] dioxine-6-carbaldehyde (1d) with hydrogen cyanide in presence of (R)-oxynitrilase (R)-Pa HNL [EC 4.1.2.10] from almonds, as a chiral catalyst, gave the optically active cyanohydrin enantiomers ( R)-2a-c, respectively. Acetone cyanohydrin (3), was also used, as a transcyanating agent, to give the same products. The racemic cyanohydrins (R,S)-2a-d have been synthesized, as well, by treating compounds 1a-d with aqueous potassium cyanide solution in presence of a saturated solution of sodium metabisulphite (Na2S2O5). The optical purity of cyanohydrins (R)-2a-c was determined through their derivatization with (S)-naproxen chloride (S)-5 to the respective diastereomers (R,2S)-6a-c which were obtained in diastereomeric excess (de) values up to 93 % (1H NMR). Heating compounds (R)-2a,b and / or their racemic analogues (R,S)-2a-c with concentrated hydrochloric acid gave the respective α-hydroxycarboxylic acids 7a-c. Moreover, reduction of cyanohydrins (R,S)-2b,c under different conditions resulted in a hydrodecyanation giving the respective primary alcohols 8a,b. Structures and configurations of the new compounds were confirmed with compatible elementary microanalyses and spectroscopic (IR, 1H NMR, 13C NMR, MS and single crystal X-ray crystallography) measurements. The antimicrobial activity of derivatives 6a-d against four bacterial species (Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa) and two fungi (Aspergillus flavus and Candida albicans) were undertaken. Moreover, compounds (R,2S)-6b, (R,2S)(S,2S)-6b and (R,2S)-6c were screened for their in virto antitumor activity against three human solid cancer cell lines (HCT 116, HepG2 and MCF-7). In general, the tested compounds were found inactive or showed weak activities in comparison with the standard drugs.
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.
Kinetic resolution of mandelate esters via stereoselective acylation catalyzed by lipase PS-30
Chen, Peiran,Yang, Wenhong
supporting information, p. 2290 - 2294 (2014/04/17)
By using lipase PS-30 as catalyst, the kinetic resolution of a series of racemic mandelate esters has been achieved via stereoselective acylation. The value of kinetic enantiomeric ratio (E) reached up to 197.5. Substituent effect is briefly discussed.
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.
Cyanative self-condensation of aromatic aldehydes promoted by VO(O iPr)3-Lewis base as a cooperative catalyst
Kodama, Koichi,Kawamata, Hiroaki,Takahashi, Naoya,Hirose, Takuji
, p. 9440 - 9446 (2013/01/15)
Self-condensation of aromatic aldehydes with trimethylsilyl cyanide proceeded by the cooperative catalytic effect of VO(OiPr)3 and a Lewis base to give the corresponding O-acylated cyanohydrins. The reaction conversion and selectivity were strongly dependent on the solvent used, the Lewis base, and the presence of oxygen. All the nine kinds of aromatic aldehydes considered herein afforded the O-acylated cyanohydrins with excellent selectivity under an O2 atmosphere.
