{"title":"Efficient Cu‐Based Mixed Oxides Catalyst for α‐Alkylation of Ketones with Alcohols","authors":"Lina Zhang , Denghong Yao , Xue Wang , Dong Zhang","doi":"10.1002/ajoc.202400350","DOIUrl":"10.1002/ajoc.202400350","url":null,"abstract":"<div><div>A series of Cu‐based mixed oxides were prepared by calcinations of corresponding CuMgAl‐layered double hydroxides precursors at different temperatures with nominal Cu/Mg/Al ratios of 1 : 1 : 2(Cu‐LDH‐1), 1 : 2 : 1(Cu‐LDH‐2),1 : 1 : 1(Cu‐LDH‐3), and 2 : 1 : 1(Cu‐LDH‐4). The synthesized catalysts were characterized using X‐ray diffraction, high‐resolution transmission electron microscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, inductively coupled plasma atomic emission spectroscopy (ICP‐AES), and N<sub>2</sub> physisorption analysis techniques. All as‐obtained catalysts showed adequate catalytic performance for the α‐alkylation of ketones with alcohols through a hydrogen autotransfer mechanism. The catalyst CuMgAl‐I‐650 (obtained by calcining Cu‐LDH‐1 at 650 °C) displayed the highest activity and selectivity. Using this catalyst system, a wide range of branched ketones were synthesized in good to excellent isolated yields. Moreover, the catalyst CuMgAl‐I‐650 could be recycled and reutilized for four cycles without any significant loss of activity and selectivity. This study provides a very simple and inexpensive catalysis based on transition metals, which are in abundance on earth.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400350"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141784138","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}
Francisco A. A. Reis , Dr. Manda Sathish , Jorge Villaseñor , Dr. Fabiane M. Nachtigall , Dr. Leonardo S. Santos
{"title":"Pd‐Monothiosquaramides: Efficient Catalysts for the Enantioselective Imine Reduction of Dihydro‐β‐Carbolines","authors":"Francisco A. A. Reis , Dr. Manda Sathish , Jorge Villaseñor , Dr. Fabiane M. Nachtigall , Dr. Leonardo S. Santos","doi":"10.1002/ajoc.202400245","DOIUrl":"10.1002/ajoc.202400245","url":null,"abstract":"<div><div>An efficient enantioselective synthesis of tetrahydro‐β‐carbolines (THBCs) using chiral metal‐monothiosquaramides (M–MTSQs) was planned. The <em>in situ</em> generated Pd/Fe‐monothiosquaramides (Pd/Fe‐MTSQs) catalysed imine reduction of dihydro‐β‐carbolines exceptionally to afford chiral THBCs with an excellent enantiomeric excess (up to 98% ee). In a catalysis study, Pd‐MTSQ <strong>12 a</strong> (10 mol%) was found to be more efficient than Pd‐MTSQ <strong>12 b</strong> and Fe‐MTSQs (<strong>13 a</strong> and <strong>13 b</strong>) for enantioselective imine reduction of DHBCs <strong>14 a</strong>–<strong>e</strong>. All the major chiral alkyl‐THBC isomers <strong>15 a</strong>–<strong>c</strong> (90% ee, 98% ee and 95% ee, respectively) were observed with <em>R</em> configuration which was explained by <em>Si</em> face hydride attack on alkyl DHBC imines (<strong>14 a</strong>–<strong>c</strong>). Surprisingly, <em>S</em> configuration was perceived for the major isomers of chiral aryl‐THBCs <strong>15 d</strong> and <strong>15 e</strong> (95% ee and 96% ee, respectively) which was rationalized by <em>Re</em> face hydride attack on aryl DHBC imines (<strong>14 d</strong> and <strong>14 e</strong>).</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400245"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141520294","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}
{"title":"Synthesis, Anticancer Evaluation, in‐silico ADMET and Molecular Docking Studies for Tailored Pyrazolo‐Benzothiazole Hybrids","authors":"Omkar Bains , Ashish Kumar , Raj Kamal , Rasdeep Kour , Simrandeep Kaur , Satwinderjeet Kaur , Raman Jangra , Purshotam Sharma , Ravinder Kumar","doi":"10.1002/ajoc.202400187","DOIUrl":"10.1002/ajoc.202400187","url":null,"abstract":"<div><div>The present article demonstrates the regioselective synthesis, characterization, and biological evaluation of eighteen novel pyrazolo‐benzothiazole hybrid molecules 5a–5r. We have utilized β,β‐ditosyloxy ketone protocol to synthesize these hybrid molecules. The synthesized compounds were tested for their <em>in‐vitro</em> antiproliferative activities using MTT assay against breast cancer (MCF‐7), cervical cancer (HeLa), and Lung cancer (A549) cell lines. Hybrid molecules 5a, 5m, 5n, and 5o with IC<sub>50</sub> values of 0.359 mM, 0.051 mM, 0.079 mM, and 0.259 mM respectively exhibited admirable growth inhibitory properties against MCF‐7 cancer cells which are even better than reference carboplatin drug having IC<sub>50</sub> (0.439 mM). Compound 5k with IC<sub>50</sub> value of 0.765 mM was found to be the most potent antiproliferative agent for the HeLa cancer cells. Moreover, hybrid molecule 5f with IC<sub>50</sub> value of 0.706 mM exhibited better inhibitory activity against A549 cancer cells in comparison to the reference carboplatin drug having IC<sub>50</sub> (0.805 mM). The mechanism of cellular toxicity was studied using the Annexin V‐FITC/PI double staining method and cell cycle assay. Molecular docking studies for all the synthesized compounds have also been performed in the binding pocket of VEGFR2 sites (PDB code: 4ASD). Finally, the ADMET profile of the potent molecules was investigated to predict their drug‐likeness behaviour.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400187"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217023","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}
Sumit Kumar , Aditi Arora , Shivani Sapra , Riya Chaudhary , Prof. Brajendra K. Singh , Dr. Sunil K. Singh
{"title":"Recent Advances in Scandium(III) Triflate Catalysis: A Review","authors":"Sumit Kumar , Aditi Arora , Shivani Sapra , Riya Chaudhary , Prof. Brajendra K. Singh , Dr. Sunil K. Singh","doi":"10.1002/ajoc.202400295","DOIUrl":"10.1002/ajoc.202400295","url":null,"abstract":"<div><div>Over the past three decades, triflate salts have emerged as crucial Lewis acid catalysts in organic synthesis, playing a significant role in cyclization, C−H bond functionalization, and various other reactions. Among these, rare‐earth triflates have garnered attention due to their water compatibility, environmental friendliness, noncorrosive nature, and reusability. In particular, scandium(III) triflate [Sc(OTf)<sub>3</sub>] stands out as a water‐resistant Lewis acid with remarkable catalytic activity in aqueous environments. Unlike typical Lewis acids such as AlCl<sub>3</sub>, BF<sub>3</sub>, and SnCl<sub>4</sub>, which are decomposed or deactivated by water, Sc(OTf)<sub>3</sub> remains stable and effective. Its exceptional Lewis acidity, resilience against hydrolysis, and recyclability make it a prominent green catalyst. The unique stability of Sc(OTf)<sub>3</sub> in water is attributed to the smaller size of scandium ions (Sc<sup>3+</sup>), enhancing its catalytic efficiency. Sc(OTf)<sub>3</sub> has a longstanding history in organic synthesis, facilitating a wide range of reactions including aldol, Michael, allylation, Friedel‐Crafts acylations, Diels‐Alder, Mannich, cycloadditions (including cyclopropanation), and cascade reactions. The increasing utilization of Sc(OTf)<sub>3</sub> over the past decade underscores the necessity for updated insights. This review provides a concise overview of the versatility of Sc(OTf)<sub>3</sub> as a catalyst, focusing on developments from 2017 to 2024.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400295"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142216916","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}
Peidong Song , Zhe Cui , Tingting Meng , Haojie Rong , Mingzhen Mao , Cuifeng Yang
{"title":"A Simple Conversion of Aldoximes to Nitriles Using Thiourea Dioxide","authors":"Peidong Song , Zhe Cui , Tingting Meng , Haojie Rong , Mingzhen Mao , Cuifeng Yang","doi":"10.1002/ajoc.202400291","DOIUrl":"10.1002/ajoc.202400291","url":null,"abstract":"<div><div>Thiourea dioxide (TDO) has been demonstrated to be an efficient reagent for the transformation of aromatic, heteroaromatic, alkenyl and aliphatic aldoximes to respective nitriles in excellent yields. Furthermore, this method has been applied to the synthesis of fungicide cyazofamid from a commercial precursor using TDO as a pivotal dehydrating and reducing reagent. This new procedure offers simple and easily reproducible technique for nitrile synthesis and highlights the synthetic utility of TDO as a versatile reagent in organic chemistry.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400291"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141754076","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}
Yun‐Meng Li , Man Jiang , Jing Zhou , Prof. Dr. Hai‐Lei Cui
{"title":"HBr/TMSO/HFIP Mediated Chemoselective Modifications of Pyrrolo[2,1‐a]Isoquinolines","authors":"Yun‐Meng Li , Man Jiang , Jing Zhou , Prof. Dr. Hai‐Lei Cui","doi":"10.1002/ajoc.202400323","DOIUrl":"10.1002/ajoc.202400323","url":null,"abstract":"<div><div>The combination of HBr, TMSO (tetramethylene sulfoxide) and HFIP (hexafluoroisopropanol) has been utilized in the modification of pyrrolo[2,1‐<em>a</em>]isoquinoline derivatives through bromination, dimerization and sulfenylation respectively. In these processes, HBr serves as the source of bromine and TMSO acts as an oxidant. HFIP also plays an essential role for the oxidative dimerization. Chemoselectivity can be easily controlled by adjusting the parameters such as reaction time, ratio of reagents and the addition of nucleophile.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400323"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217014","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}
Dharti Mistry , Nikunjana Benjamin Macwan , Payal Malvi , Dandamudi V. Lenin
{"title":"A Simple and Facile Conjugate Addition of Cyclic and Acyclic 1,3‐Diketones to β‐Nitrostyrenes","authors":"Dharti Mistry , Nikunjana Benjamin Macwan , Payal Malvi , Dandamudi V. Lenin","doi":"10.1002/ajoc.202400355","DOIUrl":"10.1002/ajoc.202400355","url":null,"abstract":"<div><div>A simple synthesis of 3‐hydroxy‐2‐(2‐nitro‐1‐arylethyl)cyclohex‐2‐en‐1‐ones, 3‐hydroxy‐5,5‐dimethyl‐2‐(2‐nitro‐1‐arylethyl)cyclohex‐2‐en‐1‐ones and 4‐hydroxy‐3‐(2‐nitro‐1‐arylethyl)pent‐3‐en‐2‐ones <em>via</em> conjugate addition of cyclic 1,3‐diketones, 1,3‐cyclohexanedione and 5,5‐dimethyl‐1,3‐cyclohexanedione and acyclic 1,3‐diketone, pentane‐2,4‐dione to β‐Nitrostyrenes were reported. This methodology is pleasing with reliability and scalability with gram scale products that can be synthesized.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400355"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142216918","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}
Wa‐Yi O , Ajcharapan Tantipanjaporn , Jie‐Ren Deng , Rui Tang , Karen Ka‐Yan Kung , Hoi‐Yi Sit , Chun‐Him Nathanael Lai , Man‐Kin Wong
{"title":"In Situ Generation of Quinoliziniums for Dual Visible Light‐Induced Gold(III)‐Catalyzed Alkynylation and Peptide Modification","authors":"Wa‐Yi O , Ajcharapan Tantipanjaporn , Jie‐Ren Deng , Rui Tang , Karen Ka‐Yan Kung , Hoi‐Yi Sit , Chun‐Him Nathanael Lai , Man‐Kin Wong","doi":"10.1002/ajoc.202400339","DOIUrl":"10.1002/ajoc.202400339","url":null,"abstract":"<div><div>A new approach of dual visible light‐induced gold(III)‐catalyzed alkynylation and its application in selective modification of alkyne‐linked peptides has been developed. The bis‐cyclometalated gold(III) complex exhibited dual roles of (1) <em>in situ</em> generation of quinolizinium‐based photosensitizer (λ<sub>em</sub>=500 – 594 nm) and (2) alkynylation of iminium ions. Under optimized conditions, alkynylated products were afforded in good yields up to 73 %. The application of this strategy in selective modification of alkyne‐linked peptides gave modified peptides in up to 67 % conversion. Our dual visible light/gold(III) catalysis exemplifies the potential of merging photocatalysis and transition metal catalysis to develop novel bioconjugation.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400339"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142227044","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}
Qian‐Qian Wu , Yan Wang , Muliang Zhang , Shi‐Kai Tian
{"title":"Direct Substitution of 2‐Aminotropones with Potassium Allyltrifluoroborates through Transition‐Metal‐Free C−N Bond Cleavage","authors":"Qian‐Qian Wu , Yan Wang , Muliang Zhang , Shi‐Kai Tian","doi":"10.1002/ajoc.202400386","DOIUrl":"10.1002/ajoc.202400386","url":null,"abstract":"<div><div>The poor nucleofugality of the amino group renders the C−N bond functionalization of primary aromatic amines highly challenging. Herein, we report a direct substitution reaction of 2‐aminotropones, bearing a unique non‐benzenoid seven‐membered aromatic ring that exists in some natural products and bioactive molecules, with potassium allyltrifluoroborates through C−N bond cleavage under transition‐metal‐free conditions. The amino group of 2‐aminotropones were directly substituted with potassium allyltrifluoroborates in the presence of sodium bicarbonate, delivering structurally diverse 2‐allyltropones in moderate to good yields. The reaction is free of directing groups, activating groups and transition metals, providing a convenient method to access substituted tropones.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400386"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217019","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}
Heba H. Mohamedy , Eman Fayad , Hanadi A. Katouah , Hua‐Li Qin
{"title":"Synthesis of Dithiocarbamate‐Functionalized Aliphatic Sulfonyl Fluoride via a One‐Pot Three‐Component Reaction","authors":"Heba H. Mohamedy , Eman Fayad , Hanadi A. Katouah , Hua‐Li Qin","doi":"10.1002/ajoc.202400269","DOIUrl":"10.1002/ajoc.202400269","url":null,"abstract":"<div><div>An eco‐friendly and efficient method was developed for synthesizing a novel class of aliphatic sulfonyl fluorides in a catalyst‐free one‐pot reaction. The new approach offers a streamlined synthesis for N‐(Substituted)‐2‐(fluorosulfonyl) ethyl carbamodithioates by combining amines, carbon disulfide, with ethenesulfonyl fluoride. The synthesized compounds were obtained in good yields under mild conditions, making this reaction a valuable tool for exploring new chemical transformations.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400269"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141929612","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}