Organic chemistry frontiers : an international journal of organic chemistry最新文献_第2页

Electrochemical carboxylation of α-fluoroalkyl cyclopropane with CO2 to mono- or difluoropentenoic acid† α-氟烷基环丙烷与CO2的电化学羧化反应制单氟或二氟戊烯酸

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-04-28 DOI: 10.1039/d5qo00223k

Nan Feng , Mengmeng Jiang , Huimin Wang , Yuqing Zhong , Ying Sun , Deyong Yang , Feng Zhou

引用次数: 0

Copper-catalyzed aryl ortho-C–H thiolation of aldehydes via a transient directing group strategy† 铜催化芳基邻碳氢硫代醛的瞬态定向基团策略

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-04-28 DOI: 10.1039/d5qo00472a

Mingshun Mei , Dongsheng Yi , Fanyi Meng , Junhao Tang , Yanghui Zhang

引用次数: 0

Enantioselective construction of cycloalkyl amines via nickel-catalysed alkene desymmetrization† 镍催化烯烃脱对称环烷基胺的对映选择性构造

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-04-28 DOI: 10.1039/d5qo00590f

Ludi Li , Bo Chen , Wenxu Cao , G. V. Surendra Babu , Weike Liao , Pengli Zhang , Guoqin Xia

引用次数: 0

Continuous 1,4/1,6- and 1,2-addition reactions combined with the skeletal rearrangement of 5aH,13H-chromeno[2,3-b]quinolizin-13-ones with isocyanides to enable the synthesis of pyrido[2,3-b]indolizines† 连续的1,4/1,6-和1,2-加成反应结合5aH，13H-chromeno[2,3-b]喹啉-13- 1与异氰酸酯的骨架重排，合成吡啶[2,3-b]吲哚嘧啶

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-04-28 DOI: 10.1039/d5qo00342c

Bi-Na Shao , Jia-Ming Yang , Li Chen , Wei-Min Zhang , Long-Kun Chen , Sheng-Jiao Yan

{"title":"Continuous 1,4/1,6- and 1,2-addition reactions combined with the skeletal rearrangement of 5aH,13H-chromeno[2,3-b]quinolizin-13-ones with isocyanides to enable the synthesis of pyrido[2,3-b]indolizines†","authors":"Bi-Na Shao , Jia-Ming Yang , Li Chen , Wei-Min Zhang , Long-Kun Chen , Sheng-Jiao Yan","doi":"10.1039/d5qo00342c","DOIUrl":"10.1039/d5qo00342c","url":null,"abstract":"<div><div>We developed a protocol for synthesizing highly functionalized pyrido[2,3-<em>b</em>]indolizines (PDIZs, ) from 5a<em>H</em>,13<em>H</em>-chromeno[2,3-<em>b</em>]quinolizin-13-ones using ((isocyanomethyl)sulfonyl)benzene derivatives. The continuous cycloaddition of [1,4], [1,6], and [1,2] bonds, along with skeletal rearrangement, was achieved by heating a mixture of substrates and in DMSO, facilitated by Cs<sub>2</sub>CO<sub>3</sub> and catalyzed by Ag<sub>2</sub>CO<sub>3</sub>. This process led to the cleavage of three bonds (C–C, C–N, and C–O) and the formation of four bonds (C–N and three C–C) in a single step, enabling the rapid conversion of tricyclic systems from 5a<em>H</em>,13<em>H</em>-chromeno[2,3-<em>b</em>]quinolizin-13-ones (CMQZs) to PDIZs. The rearrangement and transformation of these scaffolds are significant for drug discovery. Additionally, the reactions can be enhanced by Ag catalysis to produce functionalized PDIZs suitable for combinatorial and parallel synthesis <em>via</em> one-pot reactions.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4818-4824"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Conformational preference of N-difluoromethylated amides: contributions of hydrogen-bonding, steric, and stereoelectronic effects† n-二氟甲基化酰胺的构象偏好：氢键、立体电子和立体电子效应的贡献

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-04-28 DOI: 10.1039/d5qo00497g

Ryu Yamasaki , Ami Tashiro , Chisaki Sato , Ai Ito , Iwao Okamoto

{"title":"Conformational preference of N-difluoromethylated amides: contributions of hydrogen-bonding, steric, and stereoelectronic effects†","authors":"Ryu Yamasaki , Ami Tashiro , Chisaki Sato , Ai Ito , Iwao Okamoto","doi":"10.1039/d5qo00497g","DOIUrl":"10.1039/d5qo00497g","url":null,"abstract":"<div><div>Fluorine, possessing the highest electronegativity among all elements, is frequently introduced to modify the structure and properties of compounds. Among fluorine-containing substituents, the difluoromethyl group is regarded as a bioisostere of a hydroxyl or isopropyl group, but its effect on the conformation of amides has not been thoroughly investigated. This study presents a detailed analysis of the conformational preferences of <em>N</em>-difluoromethylated amides and the effects of the difluoromethyl group, focusing on hydrogen-bonding, steric and stereoelectronic effects. <em>N</em>-Difluoromethylated amides were synthesized directly from amides using TMSCF<sub>2</sub>Br and <em>t</em>BuONa as a base. NMR analysis revealed that <em>N</em>-difluoromethylated anilides preferentially adopt <em>cis</em> conformation, whereas a phenylalanine derivative favors <em>trans</em> conformation. DFT calculations suggest that the difluoromethyl group interacts with both the carbonyl group and a phenyl group, but repulsion between the carbonyl oxygen and phenyl group and <figure><img></figure> interaction play major roles in determining the conformational preferences. In addition, the <em>trans</em> conformer of the <em>N</em>-difluoromethylated phenylalanine derivative is stabilized by electron donation from fluorine, enhancing amide resonance.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4834-4841"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872745","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Machine learning-guided protein engineering to improve the catalytic activity of transaminases under neutral pH conditions† 以机器学习为指导的蛋白质工程改善转氨酶在中性pH值条件下的催化活性

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-04-28 DOI: 10.1039/d5qo00423c

Si-Han Liu , Ligai Bai , Xu-Dong Wang , Qi-Qiang Wang , De-Xian Wang , Uwe T. Bornscheuer , Yu-Fei Ao

{"title":"Machine learning-guided protein engineering to improve the catalytic activity of transaminases under neutral pH conditions†","authors":"Si-Han Liu , Ligai Bai , Xu-Dong Wang , Qi-Qiang Wang , De-Xian Wang , Uwe T. Bornscheuer , Yu-Fei Ao","doi":"10.1039/d5qo00423c","DOIUrl":"10.1039/d5qo00423c","url":null,"abstract":"<div><div>Biocatalysis provides an eco-friendly and efficient method for the synthesis of fine chemicals, pharmaceuticals, and biofuels. However, the catalytic performance of enzymes is greatly reduced when they react under non-optimal pH conditions. Despite efforts in protein engineering to improve enzymatic pH dependence, predicting and optimizing catalytic activity under various pH conditions remain challenging. Recent advancements in machine learning (ML) provide a promising solution by enabling data-driven predictions of enzyme properties, thus reducing the need for labor-intensive experiments. This study aims to enhance enzyme activity and regulate pH dependence through ML-guided protein engineering. Using a transaminase from <em>Ruegeria</em> sp. TM1040 as the mutation template, we first collected high-quality experimental data from a series of variants by measuring their activity under a series of pH conditions. Based on these data, we developed an ML model to predict catalytic activity under different pH conditions. This work provides a powerful ML tool to guide the rational design of variants, which showed improved activity (up to 3.7-fold compared to the starting variant) at pH 7.5, and offers a data-driven protein engineering strategy to achieve co-optimization of enzyme activity and pH dependence, demonstrating the potential of ML to accelerate enzyme engineering for industrial applications.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4788-4793"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857513","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Metal- and base-free spirocyclization of alkylidene oxindoles via photo- and mechanochemically-generated nitrile ylides and nitrile imines as 1,3-dipoles† 光化学和机械化学合成的腈酰亚胺和腈亚胺作为1,3偶极子的烷基二烯氧吲哚的金属和无碱螺旋环化反应

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-04-28 DOI: 10.1039/d5qo00851d

Shweta Singh , Roopam Pandey , Varun Christopher , Mahesh Kumar Ravva , Rakesh Ganguly , Subhabrata Sen

引用次数: 0

Enantioselective and diastereodivergent construction of oxindole–pyrazolone conjugates bearing an alkenyl substituted quaternary chlorinated stereogenic centre† 含烯基取代的四氯代立体中心的氧吲哚-吡唑酮缀合物的对映选择性和非对映发散性构造

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-04-28 DOI: 10.1039/d5qo00499c

Jiapei Chen , Xusheng Duan , Mengyuan Wu , Guishun Bai , Jianwei Chen , Xuanrong Sun , Jean Rodriguez , Damien Bonne , Hong Wang , Xiaoze Bao

{"title":"Enantioselective and diastereodivergent construction of oxindole–pyrazolone conjugates bearing an alkenyl substituted quaternary chlorinated stereogenic centre†","authors":"Jiapei Chen , Xusheng Duan , Mengyuan Wu , Guishun Bai , Jianwei Chen , Xuanrong Sun , Jean Rodriguez , Damien Bonne , Hong Wang , Xiaoze Bao","doi":"10.1039/d5qo00499c","DOIUrl":"10.1039/d5qo00499c","url":null,"abstract":"<div><div>Chlorinated stereogenic carbon centres are important elements both in pharmaceutical reagents and synthetic intermediates. Herein, a novel methodology is reported for the construction of a rarely developed alkenyl substituted quaternary chlorinated stereogenic centre, featured in oxindole and pyrazolone pharmacophores. Remarkably, the configuration of the double bond was switchable <em>via</em> the combination of a suitable base and solvent. In addition, the enantioselective synthesis of <em>Z</em>-type products was achieved with natural quinidine as a catalyst, affording the chlorinated products in excellent yields and stereoselectivities. Preliminary <sup>1</sup>H-NMR titration was studied to gain insights into the control of the double bond's configuration. Moreover, the anti-tumour activity against the A549 cell-line of these newly synthesized chemical entities was evaluated, and the product (<em>E</em>)- was revealed to be a promising anti-tumour agent.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4852-4861"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143885183","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis of quinoline derivatives by palladium-catalyzed isocyanide insertion/undirected C(sp2)–H functionalization/[4 + 1] cyclization reactions involving aryl isocyanide† 钯催化异氰酸芳基插入/无向C（sp²）-H功能化/[4+1]环化反应合成喹啉衍生物

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-04-28 DOI: 10.1039/d5qo00349k

Shan-Shan Liu , Yong-Jie Wu , Jiang-Nan Zheng , Zhi-Lin Ren , Shao-Jie Jiang , Jun Wu , Ke-Ji Li , Ping He , Long Wang

引用次数: 0

A general protocol for efficient construction of perfluoro-tert-butyl alkynes with (perfluoro-tert-butyl)propiolic acid† 用（全氟叔丁基）丙酸高效构造全氟叔丁基炔的一般方案

Organic chemistry frontiers : an international journal of organic chemistry Pub Date : 2025-04-28 DOI: 10.1039/d5qo00601e

Zhiqiang Wei , Guangxing Gu , Wei Zhang , Yanchuan Zhao , Jinbo Hu

{"title":"A general protocol for efficient construction of perfluoro-tert-butyl alkynes with (perfluoro-tert-butyl)propiolic acid†","authors":"Zhiqiang Wei , Guangxing Gu , Wei Zhang , Yanchuan Zhao , Jinbo Hu","doi":"10.1039/d5qo00601e","DOIUrl":"10.1039/d5qo00601e","url":null,"abstract":"<div><div>The perfluoro-<em>tert</em>-butyl group (PF<em>t</em>B) stands out, in part, due to its unparalleled analytical capabilities, as an indispensable functional group for sensing and imaging within biological systems. Although previously we have accomplished the introduction of the perfluoro-<em>tert</em>-butyl group into sp<sup>3</sup>-and sp<sup>2</sup>-carbons, the perfluoro-<em>tert</em>-butylation of sp-carbon remains a challenging task. In this study, we develop a versatile method to construct structurally diverse PF<em>t</em>B-substituted alkynes, utilizing (perfluoro-<em>tert</em>-butyl)propiolic acid (PF<em>t</em>PA) as a new reagent. PF<em>t</em>PA is easy to synthesize and can undergo Pd/Cu-catalyzed decarboxylative coupling with a wide array of (aryl, alkyl, alkenyl, and alkynyl) halides and triflates. This synthetic protocol is not only high-yielding but also compatible with various functional groups. Furthermore, we demonstrate the potential of this new synthetic protocol by developing a <sup>19</sup>F-labeled probe that is proficient in distinguishing analytes with distal chiral centers.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 17","pages":"Pages 4773-4779"},"PeriodicalIF":0.0,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862651","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0