Thomas J. Hitchings, Helen M. Wickins, Lydia G. Burley, Silvia C. Capelli, Franz Demmel, Anthony E. Phillips, Paul Hodgkinson, Paul J. Saines
{"title":"Probing the Structure and Dynamics of the [NH4]M(HCO2)3 Ferroelectric Phases: Dielectric Relaxation through Orientational Disorder†","authors":"Thomas J. Hitchings, Helen M. Wickins, Lydia G. Burley, Silvia C. Capelli, Franz Demmel, Anthony E. Phillips, Paul Hodgkinson, Paul J. Saines","doi":"10.1002/cjoc.202401192","DOIUrl":"https://doi.org/10.1002/cjoc.202401192","url":null,"abstract":"<p>Neutron diffraction studies of the low-temperature relaxor ferroelectric phases of [NH<sub>4</sub>]M(HCO<sub>2</sub>)<sub>3</sub>, where M = Mn<sup>2+</sup> and Zn<sup>2+</sup>, show that a third of the NH<sub>4</sub><sup>+</sup> cations remain subtly structurally disordered to low temperature. All NH<sub>4</sub><sup>+</sup> cations within the channels are well separated from each other, with significant hydrogen bonds only with the anionic M(HCO<sub>2</sub>)<sub>3</sub> framework. Complementary studies of the dynamics using <sup>2</sup>H solid state NMR and quasielastic neutron scattering indicate significant rotational motion in both paraelectric and ferroelectric phases, which evolves gradually with increasing temperature with no abrupt change at the phase transition. Nudged elastic band calculations suggest that the activation barrier for flipping between “up” and “down” orientations of the NH<sub>4</sub><sup>+</sup> cations is low in the ferroelectric phase, with the NH<sub>4</sub><sup>+</sup> cations primarily interacting with the framework rather than neighbouring NH<sub>4</sub><sup>+</sup> cations. It is likely this motion that is responsible for scrambling the NH<sub>4</sub><sup>+</sup> cation orientation locally in the ferroelectric phase. We propose that this disorder, with the same basic motion active above and below the phase transition, induces the significant dielectric relaxation in these materials. This suggests that <i>orientational</i> disorder may be an effective substitution for <i>compositional</i> disorder commonly associated with relaxor ferroelectrics in molecular materials.</p><p>\u0000 </p>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 10","pages":"1190-1198"},"PeriodicalIF":5.5,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cjoc.202401192","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143835841","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Development of Silyl-Protected Phosphoramidite Building Blocks for Short ssDNA Synthesis†","authors":"Jia-Yi Liu, Yu-Ting He, Xue-Qiang Wang, Yuntian Zhu","doi":"10.1002/cjoc.202500078","DOIUrl":"https://doi.org/10.1002/cjoc.202500078","url":null,"abstract":"<div>\u0000 \u0000 <p>To overcome the depurination challenges associated with classical DNA synthesis methods, this study introduces a novel approach using fluoride-sensitive, triisopropylsilyl (TIPS)-protected phosphoramidite monomers for the efficient synthesis of short single-stranded DNA. The bulky TIPS group selectively protects the 5'-hydroxyl group of nucleosides and can be rapidly removed under mild, non-acidic conditions using fluoride ions, minimizing side reactions. Four novel TIPS-protected phosphoramidite monomers were synthesized and characterized, achieving >99% deprotection efficiency. These monomers were applied to the solid-phase synthesis of a 5-mer ssDNA sequence, yielding an overall efficiency of 99% for each cycle. The strategy demonstrates significant potential for improving the reliability and scalability of oligonucleotide synthesis, offering a promising alternative for applications in synthetic biology and nucleic acid research.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 11","pages":"1293-1298"},"PeriodicalIF":5.5,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143896873","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chunzhe Pei, Shanglin Han, Hanxuan Wu, Bin Li, Baiquan Wang
{"title":"Nickel-Catalyzed LiCl-Controlled Switchable Carboxylation of Aryl C—F Bonds with One or Two Molecules of CO2","authors":"Chunzhe Pei, Shanglin Han, Hanxuan Wu, Bin Li, Baiquan Wang","doi":"10.1002/cjoc.202401208","DOIUrl":"https://doi.org/10.1002/cjoc.202401208","url":null,"abstract":"<div>\u0000 \u0000 <p>The use of CO<sub>2</sub> as a renewable C1 source for the synthesis of value-added chemicals can contribute to a more sustainable chemistry. In this work, a nickel-catalyzed amide-directed carboxylation of aryl C−F bonds with CO<sub>2</sub> has been developed. The reaction is switchable controlled by LiCl to react with one or two molecules of CO<sub>2</sub> to afford valuable phthalimides or α-hydroxycarboxylic acid derivatives. Further study shows that the reaction is a step-by-step process. The first step is a nickel-catalyzed carboxylation of aryl C−F bonds with CO<sub>2</sub> and tandem cyclization to afford phthalimides. The second step is a nickel-catalyzed C−N bond carboxylation of phthalimides with CO<sub>2</sub>, and intramolecular nucleophilic addition of amide anion to the carbonyl. The carboxylation of phthalimides with CO<sub>2</sub> is also developed based on this reaction. The work features inert C−F bond functionalization, amide C−N bond activation, and multiple CO<sub>2</sub> incorporation. Mechanistic studies indicate that the azanickelacycle intermediates play an important role, and LiCl facilitates the reduction of Ni(II) to Ni(I) and promotes the carboxylation with the second molecule of CO<sub>2</sub>. This protocol provides an efficient route for C−F bond functionalization under mild conditions via the chemical fixation of one or two molecules of CO<sub>2</sub>.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 11","pages":"1255-1262"},"PeriodicalIF":5.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143896918","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ziyang Wang, Xin-Xin Zhang, Yidan Sun, Hanliang Zheng, Xin Li
{"title":"Enantioselective Synthesis of Planar/Multiple Chiral [n]Cyclophanes through Asymmetric Allylation","authors":"Ziyang Wang, Xin-Xin Zhang, Yidan Sun, Hanliang Zheng, Xin Li","doi":"10.1002/cjoc.202500010","DOIUrl":"https://doi.org/10.1002/cjoc.202500010","url":null,"abstract":"<div>\u0000 \u0000 <p>Planar-chiral cyclophanes with carbon-centered chirality are important targets in natural products and pharmaceuticals. However, synthesizing such planar chiral cyclophanes with two stereogenic elements via a one-step asymmetric reaction remains a formidable challenge. Herein, we present an efficient kinetic resolution method for synthesizing planar-chiral [<i>n</i>]cyclophanes with carbon-centered chirality. This is achieved through the enantioselective allylation of racemic aldehyde [<i>n</i>]cyclophanes catalyzed by Bi(OAc)<sub>3</sub> and chiral phosphoric acid. The reaction delivers planar-chiral [<i>n</i>]cyclophanes and multiple chiral [<i>n</i>]cyclophanes with high yields and excellent enantioselectivities, showcasing remarkable kinetic resolution efficiency (<i>s</i> factor up to 292). The broad substrate scope, scalability, and potential for derivatization highlight the value of this methodology. DFT calculations have also been performed to provide insights into the origin of the experimentally observed diastereo- and enantioselectivity for this reaction.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 11","pages":"1263-1270"},"PeriodicalIF":5.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143896933","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Selective 6π-Electrocyclization of N-Vinyl-α,β-Unsaturated Nitrones to Prepare Polysubstituted Pyridine Derivatives","authors":"Li-Yao Ding, Yan-Jiao Lu, Jin-Hong Pang, Hai-Fang Lin, Chun-Hua Chen, Hong-Yan Bi, Dong-Liang Mo","doi":"10.1002/cjoc.202401287","DOIUrl":"https://doi.org/10.1002/cjoc.202401287","url":null,"abstract":"<div>\u0000 \u0000 <p>Herein, we have developed a facile method for the synthesis of various polysubstituted pyridine derivatives through selective 6π-electrocyclization of <i>N</i>-vinyl-<i>α</i>,<i>β</i>-unsaturated nitrones. It was found that gold catalysts promoted carbon-6π-electrocyclization of <i>N</i>-vinyl-<i>α</i>,<i>β</i>-unsaturated nitrones to afford 6-alkenyl pyridine <i>N</i>-oxides in 43%—75% yields, whereas copper catalysts facilitated oxygen-6π-electrocyclization to give 6-epoxy pyridines in 41%—83% yields. The present method features broad substrate scope, good functional group tolerance, high cyclization selectivity, and diversity of polysubstituted pyridine scaffolds.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 11","pages":"1287-1292"},"PeriodicalIF":5.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143896998","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Neutral Chalcogen Bonding Enabled Photoinduced Cross-Electrophile C—S/Se Coupling of Aryl Iodides via SRN1 Process","authors":"Yong-Liang Tu, Xiang Li, Bei-Bei Zhang, Gui-Ying Fu, Ling Zhou, Wei Gong, Xiang-Yu Chen","doi":"10.1002/cjoc.202401197","DOIUrl":"https://doi.org/10.1002/cjoc.202401197","url":null,"abstract":"<div>\u0000 \u0000 <p>Cross-coupling reactions between aryl halides and thiolates or selenolates typically require transition metals, photocatalysts, strong bases, or/and malodorous thiols/selenols, with various mechanisms proposed. This study aims to leverage a new application of neutral ChB to address these challenges and enable a very simple photoinduced cross-electrophile C—S/Se coupling using readily available chalcogen electrophiles. Mechanistic investigations have revealed the important role of neutral ChB in facilitating single electron transfer processes, thereby enabling the generation of thiolates/selenolates from stable chalcogen electrophiles and <i>α</i>-aminoalkyl radicals, which possess the capability to abstract halogen atoms from aryl iodides. Moreover, the study provided support for the radical nucleophilic substitution mechanism.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 11","pages":"1299-1305"},"PeriodicalIF":5.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143896917","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"A Divergent Synthesis of Spiroindenes via Ligand-Controlled [3+2]/[4+2] Cycloadditions of Zwitterionic π-Propargyl Palladium Species with Benzofulvenes","authors":"Yongjie Long, Xianhua Zhong, Min Shi, Yin Wei","doi":"10.1002/cjoc.202401301","DOIUrl":"https://doi.org/10.1002/cjoc.202401301","url":null,"abstract":"<div>\u0000 \u0000 <p>A divergent synthesis of spiroindenes through a palladium catalyzed cycloaddition between zwitterionic π-propargyl palladium species and benzofulvenes in moderate to good yields has been disclosed along with good functional group compatibility and a broad substrate universality. This protocol features a highly regioselective switchable process between [3+2] and [4+2] cycloadditions controlled by phosphine ligands with different bite angles. The reaction mechanism has been clarified by mechanistic studies and DFT calculations, rendering that the coordination modes of the ligands with the substrates and the bite angle of the ligands play critical roles in the product regioselectivity.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 10","pages":"1181-1189"},"PeriodicalIF":5.5,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143836202","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Inside Cover Picture","authors":"","doi":"10.1002/cjoc.202590072","DOIUrl":"https://doi.org/10.1002/cjoc.202590072","url":null,"abstract":"<p>Enhanced H₂ dissociation and H spillover facilitates the <i>in situ</i> generation of Fe<sup>0</sup> at the Cu/Fe<sub>3</sub>O<sub>4</sub> catalyst interfaces, which promotes C<sub>2</sub>–C<sub>3</sub> production through a photothermal CO hydrogenation pathway powered by solar energy. More details are discussed in the article by Zhong <i>et al</i>. on pages 791—797.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 7","pages":"734"},"PeriodicalIF":5.5,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cjoc.202590072","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143521942","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Pd(II)-Catalyzed Selective [4+2] Benzannulations of Pyridones with Alkenes: Diversity-Oriented Synthesis of a Novel Fluorescent Quinolinone","authors":"Yiwei Xu, Yuanyuan Wang, Jing Li, Jinxiang Ye, Hui Miao, Qianwen Gao, Chenggui Wu","doi":"10.1002/cjoc.202500045","DOIUrl":"https://doi.org/10.1002/cjoc.202500045","url":null,"abstract":"<div>\u0000 \u0000 <p>Herein, an intermolecular palladium(II)-catalyzed regioselective [4+2] benzannulation reaction capable of converting 2-pyridones into quinolinones was developed using electron-deficient alkenes as two-carbon units. An examination of the reaction mechanism indicated that the extension from 2-pyridone to quinolinone was likely facilitated through a series of sequential C—H activation reactions or 6π electrocyclization, culminating in dehydrogenative aromatization. This method of diversity-oriented synthesis of quinolinone derivatives is characterized by a broad substrate scope, atom economy, and excellent chemical selectivity. In addition, these quinolinone derivatives exhibit fluorescent absorption within the visible-light spectrum, which makes them suitable candidates for the development of innovative fluorescent probes.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 11","pages":"1239-1245"},"PeriodicalIF":5.5,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143897232","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Direct Decarboxylative Phosphorylation of α-Amino Acids via Continous-Flow Electrochemistry","authors":"Zhao-Yu Li, Na Chen, Hai-Chao Xu","doi":"10.1002/cjoc.202400256","DOIUrl":"https://doi.org/10.1002/cjoc.202400256","url":null,"abstract":"<div>\u0000 \u0000 <p>Herein we present a novel electrochemical method for the direct decarboxylative phosphorylation of α-amino acids to α-amino phosphonates, a key structural element in various biologically active compounds. This method bypasses the need for strong chemical oxidants and 2-step processes involving preliminary conversions, making it a more straightforward synthetic tool. Key to the success of the method is to establish a microenvironment on the anode surface in an acidic solution to facilitate selective anodic decarboxylation and subsequent C–P formation. The electrosynthetic process in continuous flow ensures benign conditions and excellent scalability through continuous production with parallel reactors.</p>\u0000 <p>\u0000 </p>\u0000 </div>","PeriodicalId":151,"journal":{"name":"Chinese Journal of Chemistry","volume":"43 10","pages":"1167-1172"},"PeriodicalIF":5.5,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143836369","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}