Chirality最新文献_第4页

Absolute Configuration Assignment From a Single Reflection Using Resonant X-Ray Diffraction 用共振x射线衍射从单反射得到绝对构型分配。

IF 2.4 4区化学

Chirality Pub Date : 2026-08-04 DOI: 10.1002/chir.70129

Anmol Andotra, Fabian Gasser, Ferdinando Malagreca, Roland C. Fischer, Yves H. Geerts, Roland Resel

{"title":"Absolute Configuration Assignment From a Single Reflection Using Resonant X-Ray Diffraction","authors":"Anmol Andotra, Fabian Gasser, Ferdinando Malagreca, Roland C. Fischer, Yves H. Geerts, Roland Resel","doi":"10.1002/chir.70129","DOIUrl":"10.1002/chir.70129","url":null,"abstract":"Determination of the absolute configuration of chiral molecules is essential across multiple scientific disciplines, as handedness determines the chiroptical, biological, and pharmaceutical properties. For crystalline materials, single crystal x-ray diffraction is the standard technique for assigning the absolute configuration. However, its application typically requires a large number of reflections and analysis of Friedel pair intensities using the Flack parameter or related approaches, such as those of Hooft or Parsons. Here, we introduce a conceptually distinct approach for determining the absolute configuration of a known crystal structure, based on the x-ray energy dependent intensity of a single Bragg reflection that is sensitive to the absolute configuration. By monitoring the variation in the intensity of a Bragg peak across an absorption edge, this method provides an unambiguous probe of chirality. The proposed approach is demonstrated for the <math>\u0000 <semantics>\u0000 <mrow>\u0000 <mn>211</mn>\u0000 </mrow>\u0000 <annotation>$$ 211 $$</annotation>\u0000 </semantics></math> reflection of a 2-(3-bromophenyl)-N,N-diisopropyl-2-oxoacetamide single crystal, showing that the absolute configuration can be reliably determined from a single reflection. To confirm the assignment of chirality and assess potential limitations, the x-ray energy dependence of additional diffraction peaks was also investigated. This method is particularly advantageous for systems with a limited number of accessible reflections, where conventional statistical methods based on Flack parameter analysis are not reliable.","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"38 8","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13434679/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148668637","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mass Spectrometry in Chiral Analysis and Synthesis 质谱法在手性分析与合成

IF 2.4 4区化学

Chirality Pub Date : 2026-07-31 DOI: 10.1002/chir.70126

Brison A. Shira, Mahdiyeh Shahi, R. Graham Cooks

{"title":"Mass Spectrometry in Chiral Analysis and Synthesis","authors":"Brison A. Shira, Mahdiyeh Shahi, R. Graham Cooks","doi":"10.1002/chir.70126","DOIUrl":"https://doi.org/10.1002/chir.70126","url":null,"abstract":"Mass spectrometry (MS) has a role to play in chiral chemistry, in part through methods based on microdroplets and non-covalent molecular clusters. High-throughput MS reaction screening and chiral anal0ysis use microdroplet sprays to perform accelerated nanoscale chemistry, including the synthesis of heterocyclics and other drug candidates using new high-throughput automated instrumentation. The kinetic method of chiral analysis measures competitive dissociation reactions of molecular clusters (usually trinary coordination complexes) to determine enantiomeric excess (e.e.). A very different molecular cluster, the serine octamer, an active research topic for two decades, may hold implications in the search for the origins of homochirality. Lastly, the recently reported direct discrimination of enantiomers using an ion trap mass spectrometer (ITMS) is revisited. These four examples, combined with recent findings concerning chiral post-translational modifications in cancer biology, represent exciting research developments that deploy the advantages of MS (throughput, molecular specificity, and sample size) to improve chiral synthesis and analysis.","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"38 8","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chir.70126","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148617376","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Chiral Resolution of Aspartic Acid Racemate by Single Crystallization With Phenylalanine as Additive 以苯丙氨酸为添加剂的单结晶手性拆分天冬氨酸消旋体

IF 2.4 4区化学

Chirality Pub Date : 2026-07-30 DOI: 10.1002/chir.70131

Xiaohong Xue, Sheng Gong, Jiali Wen, Zhentong Guan, Sichang Peng, Zongxia Guo

{"title":"Chiral Resolution of Aspartic Acid Racemate by Single Crystallization With Phenylalanine as Additive","authors":"Xiaohong Xue, Sheng Gong, Jiali Wen, Zhentong Guan, Sichang Peng, Zongxia Guo","doi":"10.1002/chir.70131","DOIUrl":"https://doi.org/10.1002/chir.70131","url":null,"abstract":"<div>\u0000 \u0000 The effective chiral resolution of amino acid racemates has important significance in fields such as medicine and pharmaceuticals. By using phenylalanine as additive, the chiral resolution of aspartic acid racemate was investigated through crystallization method. It reveals that the enantiomeric excess of the crystalline product is affected by the seeding temperature, crystallization temperature, crystallization time, seed dosage, phenylalanine dosage, and the relative supersaturation. Under optimized condition, the average enantiomeric excess could reach 85% after a single crystallization in water. The excess enantiomer of the crystalline product is determined by the configuration of phenylalanine. The enantiomeric excess and the excess enantiomer were confirmed by chiral high performance liquid chromatography. The powder X-ray diffraction and Fourier transform infrared spectral results show that conglomerate was formed in the crystalline product. Seed and additive both play great role in the chiral resolution. The findings could give inspirations for efficient resolution of aspartic acid racemate into enantiopure compounds.\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"38 8","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148617180","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Diastereotopic Fluorines of CF2 Group as Stereochemical Probes for Empirical 19F NMR-Based Assignment of Absolute Configuration of an Epimeric Center. 21,21-Difluorothevinols CF2非对映位氟基团作为立体化学探针的经验19F核磁共振外映中心绝对构型分配。21,21-二氟乙烯醇。

IF 2.4 4区化学

Chirality Pub Date : 2026-07-27 DOI: 10.1002/chir.70127

M. V. Zelentsova, Zh. A. Lopantseva, M. I. Godovikova, A. F. Smol'yakov, A. N. Rodionov, S. K. Moiseev

{"title":"Diastereotopic Fluorines of CF2 Group as Stereochemical Probes for Empirical 19F NMR-Based Assignment of Absolute Configuration of an Epimeric Center. 21,21-Difluorothevinols","authors":"M. V. Zelentsova, Zh. A. Lopantseva, M. I. Godovikova, A. F. Smol'yakov, A. N. Rodionov, S. K. Moiseev","doi":"10.1002/chir.70127","DOIUrl":"10.1002/chir.70127","url":null,"abstract":"<div>\u0000 \u0000 The chemical shifts of diastereotopic fluorine atoms in compounds of the formula ArC(R)(OH)CF2R′ with unchanged R and R′ are weakly dependent on the substituents on the aryl group. In the presence of a chiral group R*, the chemical shifts of the fluorine atoms differ in the epimers. This feature can be used for the simple empirical assignment of an absolute configuration of the benzylic epimeric center in newly synthesized compounds of the formula ArC(R*)(OH)CF2R′ using routine 19F or 19F{1H} NMR spectroscopy. In this work, this simple approach was applied to assign the configuration of the chiral center at C(20) in 20-aryl- and 20-alkyl-21,21-difluorothevinols, opioid receptor ligands. The results obtained by 19F{1H} NMR were validated by correlation with the X-ray diffraction data. The method also enables configurational assignment of the corresponding 21,21-difluoroorvinols, opioid ligands with higher efficacy, as they are usually obtained from the corresponding thevinols via the 3-O-demethylation reaction not affecting the chiral center at C(20).\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"38 8","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148599782","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Enantioselective Resolution of β- and γ-Lactams by a Single Amidase From Rhodococcus baikonurensis Enables Efficient Access to Key Intermediates for Paclitaxel and Carbocyclic Nucleosides 单酶对β-内酰胺和γ-内酰胺的对映选择性分离使紫杉醇和碳环核苷的关键中间体获得高效。

IF 2.4 4区化学

Chirality Pub Date : 2026-07-26 DOI: 10.1002/chir.70117

Shaozhou Zhu, Hang Wang, Linlin Yang, Jiabei Sun, Jing Yao, Hongxia Li, Haiwei Huang

{"title":"Enantioselective Resolution of β- and γ-Lactams by a Single Amidase From Rhodococcus baikonurensis Enables Efficient Access to Key Intermediates for Paclitaxel and Carbocyclic Nucleosides","authors":"Shaozhou Zhu, Hang Wang, Linlin Yang, Jiabei Sun, Jing Yao, Hongxia Li, Haiwei Huang","doi":"10.1002/chir.70117","DOIUrl":"10.1002/chir.70117","url":null,"abstract":"<div>\u0000 \u0000 Enantiomerically pure β- and γ-lactams are vital chiral building blocks widely used in the synthesis of antiviral and anticancer drugs. However, producing them on a large scale through chemical synthesis and enantiomeric separation is both expensive and harmful to the environment. Using integrative bioinformatics, we identified a new signature amidase, Rb-Ami, from the haloalkaliphilic bacterium Rhodococcus baikonurensis. The Rb-ami gene was cloned and successful expressed in Escherichia coli BL21. Soluble and active recombinant enzyme was obtained, and in vitro studies show that this enzyme can efficiently catalyze the enantioselective hydrolysis of different lactam substrates. Specifically, Rb-Ami can effectively resolve racemic mixtures of 3-hydroxy-4-phenylazetidin-2-one (β-lactam) and 2-azabicyclo[2.2.1]hept-5-en-3-one (γ-lactam), delivering enantiomeric excesses greater than 99.0% and yields above 49.0%. To our knowledge, this is the first reported amidase exhibiting both γ-lactamase and β-lactamase activities, and the first β-lactamase used for the kinetic resolution of racemic 3-hydroxy-4-phenylazetidin-2-one. This enzymatic method provides a highly efficient and eco-friendly approach for producing the paclitaxel side chain and precursors of carbocyclic nucleoside antivirals.\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"38 8","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148590651","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Comparative Study of the Influence of Water and Temperature on the Racemization of Five- and Six-Membered l-Alanine-Derived Imides 水和温度对五元和六元l-丙氨酸衍生亚胺消旋化影响的比较研究

IF 2.4 4区化学

Chirality Pub Date : 2026-07-20 DOI: 10.1002/chir.70124

Diksha U. Sawant, William Chant, Peter Halat, Ekaterina I. Izgorodina, David R. Turner

引用次数: 0

In Silico Analysis of Enantioselective Binding of Pomalidomide Targets for Multiple Myeloma 波马度胺靶向治疗多发性骨髓瘤的对映选择性结合的计算机分析。

IF 2.4 4区化学

Chirality Pub Date : 2026-07-18 DOI: 10.1002/chir.70125

Gyan Vardhan, Vikas Kumar, Ashish Kumar, Shailendra Handu, Puneet Dhamija

{"title":"In Silico Analysis of Enantioselective Binding of Pomalidomide Targets for Multiple Myeloma","authors":"Gyan Vardhan, Vikas Kumar, Ashish Kumar, Shailendra Handu, Puneet Dhamija","doi":"10.1002/chir.70125","DOIUrl":"10.1002/chir.70125","url":null,"abstract":"<div>\u0000 \u0000 Pomalidomide is a 2nd-generation chiral immunomodulatory (IMiDs) drugs and have antiangiogenic activity. Despite being teratogenic, it has been shown to be effective in treating multiple myeloma. Enantioselectivity, chemical structure, and biological activity have been investigated using molecular docking. In silico docking simulations to confirm the enantioselective binding of pomalidomide to immunomodulator targets, namely, CRBN, TNF- α11, Pg G/H synthase 2, and Cadeherin-5 Protein. The protein was preprocessed using hydrogen addition, disulphide treatment, and bond order assignment. The Ligand Preparation Module was used to optimize all of the chosen ligands, and OPLS3e Forcefield was used to optimize the geometry. Site map analysis module was used to determine the top-ranked receptor binding sites for the enzymes. Molecules were docked by using Schrodinger 2020_3 software. Docking study confirms the enantioselective binding of pomalidomide to immunomodulator targets (CRBN, TNF-α_11, Pg G/H synthase 2, and Cadeherin-5 Protein). Out of all four targets S- (−) enantiomer of pomalidomide had significant binding with CRBN and TNF-α 11, while R-(+)enantiomer of pomalidomide had significant binding with Pg G/H synthase 2, and Cadeherin-5 Protein. The result suggests that, chemical interactions of S-enantiomer of pomalidomide have better binding with residues at the active site of CRBN and TNF-α 11. This concludes that S-enantiomer of pomalidomide could be a better choice for multiple myeloma therapy.\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"38 8","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148469351","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Consequences of Mechanical Bonding on the Optical Activity of Cyclo[18]carbon Rings 机械键合对环b[18]碳环旋光性的影响。

IF 2.4 4区化学

Chirality Pub Date : 2026-07-18 DOI: 10.1002/chir.70123

Afton Gustafson, Sophia Sburlati, Bart Kahr

{"title":"Consequences of Mechanical Bonding on the Optical Activity of Cyclo[18]carbon Rings","authors":"Afton Gustafson, Sophia Sburlati, Bart Kahr","doi":"10.1002/chir.70123","DOIUrl":"10.1002/chir.70123","url":null,"abstract":"<div>\u0000 \u0000 The computed nonresonant optical activity of pairs of cyclo[18]carbon rings, linked and unlinked with the same symmetry, D2d, are compared. For optically active, non-enantiomorphous systems, we emphasize that the observables computed here can only be measured for oriented molecules in suitably dissymmetric configurations. Mechanically bonded linked rings have one independent gyration tensor eigenvalue, ±16 bohr4. Breaking the mechanical bond and thereby unlinking the rings, while maintaining noncovalent contact, triples the gyration, resulting in an eigenvalue of ±54 bohr4. Of the excited states with B2 and E symmetry that contribute to the optical activity, the B2 states dominate the overall response of the link and unlink. The responses of selected low-energy states, that mimic the responses of a more comprehensive sum over many states, narrate in part the paradox that two optically inactive monomers in close proximity are more chiroptically scattering than the linked pair. The behavior described here underscores the importance of noncovalent interactions in optical activity.\u0000 </div>","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"38 8","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148469367","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Green Chiral HPLC Method for Lumefantrine Analysis: Method Development, Greenness Assessment, and Computational Studies 绿色手性高效液相色谱法分析氨芳碱：方法发展，绿色评价和计算研究。

IF 2.4 4区化学

Chirality Pub Date : 2026-07-16 DOI: 10.1002/chir.70122

Amanda Mohr, Gustavo Machado das Neves, Érika Segala, Vera Lucia Eifler-Lima, Martin Steppe

{"title":"Green Chiral HPLC Method for Lumefantrine Analysis: Method Development, Greenness Assessment, and Computational Studies","authors":"Amanda Mohr, Gustavo Machado das Neves, Érika Segala, Vera Lucia Eifler-Lima, Martin Steppe","doi":"10.1002/chir.70122","DOIUrl":"10.1002/chir.70122","url":null,"abstract":"Currently, greening analytical methods have become of great interest to ensure operators' and environment health. Chiral analysis can commonly employ hazardous chemicals and large quantities of waste. In this context, this study presents a green chiral high-performance liquid chromatography (HPLC) method for the determination of lumefantrine (LUME) enantiomers. Chromatographic enantioseparation was achieved on a Chiralpak AD column with a mobile phase composed of ethanol at a flow rate of 1 mL/min. The effects of column temperature on the retention of the enantiomers were investigated, and the analysis temperature was set at 35°C. The method greenness profile was assessed using the Analytical GREEnness (AGREE) and Analytical Green Star Area (AGSA) metrics by which the method proved to be eco-friendly. The method was validated, showing adequate selectivity, linearity, precision, accuracy, and robustness over the range of 80–120 μg/mL per enantiomer. Electronic circular dichroism (ECD) analysis proposed that the first eluted peak was the R-enantiomer and the second eluted peak was the S-enantiomer. Molecular docking studies suggested that LUME may interact mainly through van der Waals and π-interactions on the Chiralpak AD. A green method was successfully developed for the chiral separation of LUME. The proposed work contributes to more environmentally friendly chiral approaches in pharmaceutical analysis.","PeriodicalId":10170,"journal":{"name":"Chirality","volume":"38 8","pages":""},"PeriodicalIF":2.4,"publicationDate":"2026-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/chir.70122","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148469348","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Convenient Strategy to Access Diverse Libraries of Amphiphilic Compounds Based on Glycopeptoids 基于糖肽类化合物的两亲性化合物文库的便捷访问策略。

IF 2.4 4区化学

Chirality Pub Date : 2026-07-09 DOI: 10.1002/chir.70121

Ludovica Dei, Stefano Cadeddu, Claude Taillefumier, Chiara Migone, Angela Fabiano, Anna Maria Piras, Maria Chiara Santangelo, Sebastiano Di Pietro, Valeria Di Bussolo, Gaetano Angelici

引用次数: 0