70-47-3Relevant articles and documents
Direct monitoring of biocatalytic deacetylation of amino acid substrates by1H NMR reveals fine details of substrate specificity
De Cesare, Silvia,McKenna, Catherine A.,Mulholland, Nicholas,Murray, Lorna,Bella, Juraj,Campopiano, Dominic J.
supporting information, p. 4904 - 4909 (2021/06/16)
Amino acids are key synthetic building blocks that can be prepared in an enantiopure form by biocatalytic methods. We show that thel-selective ornithine deacetylase ArgE catalyses hydrolysis of a wide-range ofN-acyl-amino acid substrates. This activity was revealed by1H NMR spectroscopy that monitored the appearance of the well resolved signal of the acetate product. Furthermore, the assay was used to probe the subtle structural selectivity of the biocatalyst using a substrate that could adopt different rotameric conformations.
Noncovalently Functionalized Commodity Polymers as Tailor-Made Additives for Stereoselective Crystallization
Wan, Xinhua,Wang, Zhaoxu,Ye, Xichong,Zhang, Jie
supporting information, p. 20243 - 20248 (2021/08/09)
Stereoselective inhibition of the nucleation and crystal growth of one enantiomer aided by “tailor-made” polymeric additives is an efficient method to obtain enantiopure compounds. However, the conventional preparation of polymeric additives from chiral monomers are laborious and limited in structures, which impedes their rapid optimization and applicability. Herein, we report a “plug-and-play” strategy to facilitate synthesis by using commercially available achiral polymers as the platform to attach various chiral small molecules as the recognition side-chains through non-covalent interactions. A library of supramolecular polymers made up of two vinyl polymers and six small molecules were applied with seeds in the selective crystallization of seven racemates in different solvents. They showed good to excellent stereoselectivity in yielding crystals with high enantiomeric purities in conglomerates and racemic compound forming systems. This convenient, low-cost modular synthesis strategy of polymeric additives will allow for high-efficient, economical resolution of various racemates on different scales.
A method of synthesizing L - asparagine (by machine translation)
-
Page/Page column 4-6, (2019/05/08)
The invention provides a method of synthesizing L - asparagine, the main technical means is to L - aspartic acid as the raw material, first to the reaction in the cauldron the pump enters methanol, then open the reaction kettle, input L - aspartic acid, cooling, subsequently drop adds the chlorination sulfoxide, generating L - aspartic acid methyl ester hydrochloride, then will be of the L - aspartic acid methyl ester hydrochloride into a reaction kettle, then to the reaction in the cauldron the pump enters the ammonia, to obtain the L - asparagine, the method generating L - aspartic acid methyl ester hydrochloride intermediate product, the intermediate product is stable structure, safe and non-toxic, for subsequent operation processing, reaction process only needs to have the participation of ammonia water, reactant complex, the small influence of the product, the method of the invention recovery of the methanol up to 99.5 - 99.9%, not only improving the intermediate the purity of the product, and also avoids the pollution of methanol, L - asparagine is finished effective content of 80 - 85%, moisture content is 15 - 18%, yield and moisture content are higher than the amount of the existing products, the method of the invention is suitable for industrial production. (by machine translation)
Colony-wise Analysis of a Theonella swinhoei Marine Sponge with a Yellow Interior Permitted the Isolation of Theonellamide i
Fukuhara, Kazuya,Takada, Kentaro,Watanabe, Ryuichi,Suzuki, Toshiyuki,Okada, Shigeru,Matsunaga, Shigeki
, p. 2595 - 2599 (2018/12/13)
There are several examples of marine organisms whose metabolic profiles differ among conspecifics inhabiting the same region. We have analyzed the metabolic profile of each colony of a Theonella swinhoei marine sponge with a yellow interior and noticed the patchy distribution of one metabolite. This compound was isolated and its structure was studied by a combination of spectrometric analyses and chemical degradation, showing it to be a congener in the theonellamide class of bicyclic peptides. Theonellamides had previously been isolated by us only from T. swinhoei with a white interior and not from those with a yellow interior.
Self-Reporting Inhibitors: A Single Crystallization Process To Obtain Two Optically Pure Enantiomers
Ye, Xichong,Cui, Jiaxi,Li, Bowen,Li, Na,Zhang, Jie,Wan, Xinhua
, p. 8120 - 8124 (2018/06/29)
Collection of two optically pure enantiomers in a single crystallization process can significantly increase the chiral separation efficiency but this is difficult to realize. Now a self-reporting strategy is presented for visualizing the crystallization process by a dyed self-assembled inhibitor made from the copolymers with tri(ethylene glycol)-grafting polymethylsiloxane as the main chain and poly(N6-methacryloyl-l-lysine) as side chains. When applied with seeds together for the fractional crystallization of conglomerates, the inhibitors can label the formation of the secondary crystals and guide the complete separation process of two enantiomers with colorless crystals as the first product and red crystals as the second. This method leads to high optical purity of d/l-Asn?H2O (99.9 % ee for d-crystals and 99.5 % for l-crystals) in a single crystallization process. It requires a small amount of additives and shows excellent recyclability.
β-Cyclodextrin Functionalized Nanoporous Graphene Oxides for Efficient Resolution of Asparagine Enantiomers
Qie, Fengxiang,Guo, Jiahui,Tu, Bin,Zhao, Xing,Zhang, Yuchun,Yan, Yong
supporting information, p. 2812 - 2817 (2018/09/12)
Efficient resolution of racemic mixture has long been an attractive but challenging subject since Pasteur separated tartrate enantiomers in 19th century. Graphene oxide (GO) could be flexibly functionalized by using a variety of chiral host molecules and therefore, was expected to show excellent enantioselective resolution performance. However, this combination with efficient enantioselective resolution capability has been scarcely demonstrated. Here, nanoporous graphene oxides were produced and then covalently functionalized by using a chiral host material-β-cyclodextrin (β-CD). This chiral GO displayed enantioselective affinity toward the l-enantiomers of amino acids. In particular, >99 % of l-asparagine (Asn) was captured in a racemic solution of Asn while the adsorption of d-enantiomer was not observed. This remarkable resolution performance was subsequently modelled by using an attach-pull-release dynamic method. We expect this preliminary concept could be expanded to other chiral host molecules and be employed to current membrane separation technologies and finally show practical use for many other racemates.
Chromatographic Resolution of α-Amino Acids by (R)-(3,3'-Halogen Substituted-1,1'-binaphthyl)-20-crown-6 Stationary Phase in HPLC
Wu, Peng,Wu, Yuping,Zhang, Junhui,Lu, Zhenyu,Zhang, Mei,Chen, Xuexian,Yuan, Liming
supporting information, p. 1037 - 1042 (2017/07/25)
Three new chiral stationary phases (CSPs) for high-performance liquid chromatography were prepared from R-(3,3'-halogen substituted-1,1'-binaphthyl)-20-crown-6 (halogen = Cl, Br and I). The experimental results showed that R-(3,3'-dibromo-1,1'-binaphthyl)-20-crown-6 (CSP-1) possesses more prominent enantioselectivity than the two other halogen-substituted crown ether derivatives. All twenty-one α-amino acids have different degrees of separation on R-(3,3'-dibromo-1,1'-binaphthyl)-20-crown-6-based CSP-1 at room temperature. The enantioselectivity of CSP-1 is also better than those of some commercial R-(1,1'-binaphthyl)-20-crown-6 derivatives. Both the separation factors (α) and the resolution (Rs) are better than those of commercial crown ether-based CSPs [CROWNPAK CR(+) from Daicel] under the same conditions for asparagine, threonine, proline, arginine, serine, histidine and valine, which cannot be separated by commercial CR(+). This study proves the commercial usefulness of the R-(3,3'-dibromo-1,1'-binaphthyl)-20-crown-6 chiral stationary phase.
Influence of the amino acid side chain on peptide bond hydrolysis catalyzed by a dimeric Zr(iv)-substituted Keggin type polyoxometalate
Ly, Hong Giang T.,Absillis, Gregory,Parac-Vogt, Tatjana N.
, p. 976 - 984 (2016/02/19)
Peptide bond hydrolysis of 18 different dipeptides, divided into four groups depending on the nature of the amino acid side chain, by the dimeric Zr(iv)-substituted Keggin type polyoxometalate (POM) (Et2NH2)8[{α-PW11O39Zr-(μ-OH)(H2O)}2]·7H2O (1) was studied by means of kinetic experiments and 1H/13C NMR spectroscopy. The observed rate constants highly depend on the bulkiness and chemical nature of the X amino acid side chain. X-Ser and X-Thr dipeptides showed increased reactivity due to intramolecular nucleophilic attack of the hydroxyl group in the side chain on the amide carbon, resulting in a reactive ester intermediate. A similar effect in which the amino acid side chain acted as an internal nucleophile was observed for the hydrolysis of Gly-Asp. Interestingly, in the presence of 1 deamidation of Gly-Asn and Gly-Gln into Gly-Asp and Gly-Glu was observed. Dipeptides containing positively charged amino acid side chains were hydrolyzed at higher rates due to electrostatic interactions between the negatively charged POM surface and positive amino acid side chains.
Enantiospecific C-H Activation Using Ruthenium Nanocatalysts
Taglang, Céline,Martínez-Prieto, Luis Miguel,Del Rosal, Iker,Maron, Laurent,Poteau, Romuald,Philippot, Karine,Chaudret, Bruno,Perato, Serge,Sam Lone, Ana?s,Puente, Céline,Dugave, Christophe,Rousseau, Bernard,Pieters, Grégory
supporting information, p. 10474 - 10477 (2015/09/02)
The activation of C-H bonds has revolutionized modern synthetic chemistry. However, no general strategy for enantiospecific C-H activation has been developed to date. We herein report an enantiospecific C-H activation reaction followed by deuterium incorporation at stereogenic centers. Mechanistic studies suggest that the selectivity for the α-position of the directing heteroatom results from a four-membered dimetallacycle as the key intermediate. This work paves the way to novel molecular chemistry on nanoparticles.
Microseiramide from the freshwater cyanobacterium Microseira sp. UIC 10445
Luo, Shangwen,Krunic, Aleksej,Chlipala, George E.,Orjala, Jimmy
, p. 47 - 52 (2015/06/08)
Abstract Microseiramide (1), a cyclic heptapeptide, was isolated from a sample of the freshwater cyanobacterium Microseira sp. UIC 10445 collected in a shallow lake in Northern Indiana. Taxonomic identification of UIC 10445 was performed by a combination of morphological and phylogenetic characterization. Phylogenetic analysis revealed that UIC 10445 was a member of the recently described genus Microseira, which is phylogenetically distinct from the morphologically similar genera, Moorea and Lyngbya. The planar structure of microseiramide (1) was determined by extensive 1D and 2D NMR experiments as well as HRESIMS analysis. The absolute configurations of amino acid residues were determined using acid hydrolysis followed by the advanced Marfey's analysis. Microseiramide (1) is the first cyclic peptide reported from a Microseira sp., and the structure of microseiramide (1) is distinct from the previously known metabolites from cyanobacteria of the genera Moorea and Lyngbya.
