16051-87-9Relevant academic research and scientific papers
MONOHYDROLYSIS OF AN ALIPHATIC DINITRILE COMPOUND BY NITRILASE FROM RHODOCOCCUS RHODOCHROUS K22
Kobayashi, Michihiko,Yanaka, Noriyuki,Nagasawa, Toru,Yamada, Hideaki
, p. 5587 - 5590 (1990)
Nitrilase from Rhodococcus rhodochrous K22 catalyzes the conversion of various aliphatic nitrile derivatives to the corresponding acids.Using this resting cells, 4-cyanobutyric acid was synthesized from glutaronitrile with 100percent molar conversion.
Enzymatic halogenation and oxidation using an alcohol oxidase-vanadium chloroperoxidase cascade
But, Andrada,van Noord, Aster,Poletto, Francesca,Sanders, Johan P.M.,Franssen, Maurice C.R.,Scott, Elinor L.
, p. 92 - 100 (2017)
The chemo-enzymatic cascade which combines alcohol oxidase from Hansenula polymorpha (AOXHp) with vanadium chloroperoxidase (VCPO), for the production of biobased nitriles from amino acids was investigated. In the first reaction H2O2 (and acetaldehyde) are generated from ethanol and oxygen by AOXHp. H2O2 is subsequently used in the second reaction by VCPO to produce HOBr in situ. HOBr is required for the non-enzymatic oxidative decarboxylation of glutamic acid (Glu) to 3-cyanopropanoic acid (CPA), an intermediate in the production of biobased acrylonitrile. It was found that during the one pot conversion of Glu to CPA by AOXHp-VCPO cascade, AOXHp was deactivated by HOBr. To avoid deactivation, the two enzymes were separated in two fed-batch reactors. The deactivation of AOXHp by HOBr appeared to depend on the substrate: an easily halogenated compound like monochlorodimedone (MCD) was significantly converted in one pot by the cascade reaction of AOXHp and VCPO, while conversion of Glu did not occur under those conditions. Apparently, MCD scavenges HOBr before it can inactivate AOXHp, while Glu reacts slower, leading to detrimental concentrations of HOBr. Enzymatically generated H2O2 was used in a cascade reaction involving halogenation steps to enable the co-production of biobased nitriles and acetaldehyde.
A bioorthogonal raman reporter strategy for SERS detection of glycans on live cells
Lin, Liang,Tian, Xiangdong,Hong, Senlian,Dai, Peng,You, Qiancheng,Wang, Ruyi,Feng, Lianshun,Xie, Can,Tian, Zhong-Qun,Chen, Xing
, p. 7266 - 7271 (2013)
Direct detection of glycans on live cells using surface-enhanced Raman scattering (SERS) has been shown. A bioorthogonal Raman reporter was directly installed onto the monosaccharide analogs. Once metabolically incorporated into cell surface glycans, the Raman reporter was detected using SERS (see picture). Copyright
Towards Preparative Chemoenzymatic Oxidative Decarboxylation of Glutamic Acid
Xu, Xiaomin,But, Andrada,Wever, Ron,Hollmann, Frank
, p. 2180 - 2183 (2020)
The chemoenzymatic oxidative decarboxylation of glutamic acid to the corresponding nitrile using the vanadium chloroperoxidase from Curvularia inaequalis (CiVCPO) as HOBr generation catalysts has been investigated. Product inhibition was identified as major limitation. Nevertheless, 1630000 turnovers and kcat of 75 s?1 were achieved using 100 mM glutamate. The semi-preparative enzymatic oxidative decarboxylation of glutamate was also demonstrated.
Unusual differences in the reactivity of glutamic and aspartic acid in oxidative decarboxylation reactions
But, Andrada,Van Der Wijst, Evie,Le N?tre, Jér?me,Wever, Ron,Sanders, Johan P. M.,Bitter, Johannes H.,Scott, Elinor L.
, p. 5178 - 5186 (2017)
Amino acids are potential substrates to replace fossil feedstocks for the synthesis of nitriles via oxidative decarboxylation using vanadium chloroperoxidase (VCPO), H2O2 and bromide. Here the conversion of glutamic acid (Glu) and aspartic acid (Asp) was investigated. It was observed that these two chemically similar amino acids have strikingly different reactivity. In the presence of catalytic amounts of NaBr (0.1 equiv.), Glu was converted with high selectivity to 3-cyanopropanoic acid. In contrast, under the same reaction conditions Asp showed low conversion and selectivity towards the nitrile, 2-cyanoacetic acid (AspCN). It was shown that only by increasing the amount of NaBr present in the reaction mixture (from 0.1 to 2 equiv.), could the conversion of Asp be increased from 15% to 100% and its selectivity towards AspCN from 45% to 80%. This contradicts the theoretical hypothesis that bromide is recycled during the reaction. NaBr concentration was found to have a major influence on reactivity, independent of ionic strength of the solution. NaBr is involved not only in the formation of the reactive Br+ species by VCPO, but also results in the formation of potential intermediates which influences reactivity. It was concluded that the difference in reactivity between Asp and Glu must be due to subtle differences in inter- and intramolecular interactions between the functionalities of the amino acids.
Photoredox Activation of Formate Salts: Hydrocarboxylation of Alkenes via Carboxyl Group Transfer
Huang, Yan,Hou, Jing,Zhan, Le-Wu,Zhang, Qian,Tang, Wan-Ying,Li, Bin-Dong
, p. 15004 - 15012 (2021/12/14)
A photoredox activation mode of formate salts for carboxylation was developed. Using a formate salt as the reductant, carbonyl source, and hydrogen atom transfer reagent, a wide range of alkenes can be converted into acid products via a carboxyl group tra
Synthesis of α-aminonitriles using aliphatic nitriles, α-amino acids, and hexacyanoferrate as universally applicable non-toxic cyanide sources
Nauth, Alexander M.,Konrad, Tim,Papadopulu, Zaneta,Vierengel, Nina,Lipp, Benjamin,Opatz, Till
supporting information, p. 4217 - 4223 (2018/09/29)
In cyanation reactions, the cyanide source is often directly added to the reaction mixture, which restricts the choice of conditions. The spatial separation of cyanide release and consumption offers higher flexibility instead. Such a setting was used for the cyanation of iminium ions with a variety of different easy-to-handle HCN sources such as hexacyanoferrate, acetonitrile or α-amino acids. The latter substrates were first converted to their corresponding nitriles through oxidative decarboxylation. While glycine directly furnishes HCN in the oxidation step, the aliphatic nitriles derived from α-substituted amino acids can be further converted into the corresponding cyanohydrins in an oxidative C-H functionalization. Mn(OAc)2 was found to catalyze the efficient release of HCN from these cyanohydrins or from acetone cyanohydrin under acidic conditions and, in combination with the two previous transformations, permits the use of protein biomass as a non-toxic source of HCN.
Fast and pH-Independent Elimination of trans-Cyclooctene by Using Aminoethyl-Functionalized Tetrazines
Sarris, Alexi J. C.,Hansen, Thomas,de Geus, Mark A. R.,Maurits, Elmer,Doelman, Ward,Overkleeft, Herman S.,Codée, Jeroen D. C.,Filippov, Dmitri V.,van Kasteren, Sander I.
supporting information, p. 18075 - 18081 (2018/11/23)
The inverse-electron-demand Diels–Alder/pyridazine elimination tandem reaction, in which the allylic substituent on trans-cyclooctene is eliminated following reaction with tetrazines, is gaining interest as a versatile bioorthogonal process. One potential shortcoming of such currently used reactions is their propensity to proceed faster and more efficiently at lower pH, a feature caused by the nature of the tetrazines used. Here, we present aminoethyl-substituted tetrazines as the first pH-independent reagents showing invariably fast elimination kinetics at all biologically relevant pH values.
A remarkable reductive dearomatization of thiophene and furan rings
Nguyen, Son T.,Ding, Xiaoyuan,Peet, Norton P.
, p. 1904 - 1908 (2013/07/26)
Reduction of a 2-nitrothiophene 4 and the corresponding 2-nitrofuran 20 with zinc and acetic acid produced a remarkable dearomatization and fragmentation reaction to give acyclic nitriles 6 and 22, respectively. The intermediate 2-aminothiophene 5 was trapped by acylation with acetic anhydride to give acetamide 7. An additional acrylonitrile intermediate 17 was also trapped by Michael addition with benzyl mercaptan to give adduct 18. An alternate synthesis of nitrile 22 produced in the reduction of nitrofuran 20 provided an authentic sample of the product. The conversion of nitroaromatic heterocycles 4 and 20 into aliphatic nitriles 6 and 22 are remarkable and unprecedented reactions. Georg Thieme Verlag Stuttgart · New York.
Synthesis of tetrazole analogues of phosphonohydroxamic acids: An attempt to improve the inhibitory activity against the DXR
Nguyen-Trung, Anh Thu,Tritsch, Denis,Grosdemange-Billiard, Catherine,Rohmer, Michel
supporting information, p. 1643 - 1647 (2013/04/10)
This work is focused on the design of new antimicrobial drugs and on the development of lipophilic inhibitors of the DXR, the second enzyme of the MEP pathway for the biosynthesis of isoprene units in most bacteria, by replacing the phosphonate group of fosmidomycin derivatives by a tetrazoyl moiety capable of multiple hydrogen bonding. The N- and C-substituted tetrazole analogues of phosphonohydroxamate inhibitors were synthesized and tested on the DXR of Escherichia coli. This work points out the hypothesis that the phosphonate/phosphate recognition site might be too rigid to accommodate other functional groups.
