{"title":"Synthesis of Optically Active Cyclam and Its Transformations","authors":"Kazuhiro Yoshida , Yuya Miwa , Yakumo Tojima , Miyuki Takahashi , Daichi Shishido","doi":"10.1002/ajoc.202400310","DOIUrl":"10.1002/ajoc.202400310","url":null,"abstract":"<div><div>Cyclam is a well‐known example of a polyaza macrocycle. However, there are few reports of its optically active versions. In this study, we synthesized highly symmetric optically active cyclam (<em>S</em>,<em>S</em>,<em>S</em>,<em>S</em>)‐5,7,12,14‐tetraphenyl‐1,4,8,11‐tetraazacyclotetradecane, which has four phenyl groups on the cyclam skeleton, and derivatized it in various ways. We were able to synthesize a chiral Cu complex, an <em>N</em>‐ethyl derivative, and a dithiourea from this optically active cyclam. The structures of the chiral Cu complex and dithiourea were verified by single‐crystal X‐ray diffraction analysis.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400310"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142216917","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}
Ekaterina E. Vinogradova , Valentina A. Karnoukhova , Prof. Angelina N. Kravchenko , Dr. Galina A. Gazieva
{"title":"Construction of New Heterocyclic System, Imidazo[4,5‐d]thiazolo[4,3‐b]oxazole, via Cascade Reaction of Thioglycolurils with α‐Bromoketones","authors":"Ekaterina E. Vinogradova , Valentina A. Karnoukhova , Prof. Angelina N. Kravchenko , Dr. Galina A. Gazieva","doi":"10.1002/ajoc.202400369","DOIUrl":"10.1002/ajoc.202400369","url":null,"abstract":"<div><div>A method for the synthesis of new heterocyclic system representatives, i. e. imidazo[4,5‐<em>d</em>]thiazolo[4,3‐<em>b</em>]oxazole derivatives, by the reaction of thioglycolurils with α‐bromoketones has been developed. The reaction includes a cascade one‐pot S‐alkylation/nucleophilic addition/ring‐opening/ring‐closing process. This protocol is compatible with a broad scope of α‐bromoketones, diastereoselectively affording diverse products with 3a<em>S</em>*,4a<em>R</em>*,8a<em>R</em>*‐imidazo[4,5‐<em>d</em>]thiazolo[4,3‐<em>b</em>]oxazole core in 40–76 % yields.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400369"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141925958","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}
Kaizhi Xv , Jiawen Yang , Xuejun Li , Ying Liang , Yingming Pan
{"title":"Ionic Liquid‐Functionalized Porous Materials for Catalyzing CO2 Cycloaddition Reaction","authors":"Kaizhi Xv , Jiawen Yang , Xuejun Li , Ying Liang , Yingming Pan","doi":"10.1002/ajoc.202400316","DOIUrl":"10.1002/ajoc.202400316","url":null,"abstract":"<div><div>Ionic liquids (ILs) are incorporated into traditional porous materials to create ILs‐functionalized porous materials, which exhibit excellent absorption capacity and good catalytic activity for CO<sub>2</sub>. As a result, they are extensively utilized in the chemical conversion of CO<sub>2</sub>. This paper specifically focuses on the utilization of ILs‐functionalized organic porous materials, ILs‐functionalized inorganic porous materials, and ILs‐functionalized organic‐inorganic hybrid porous materials in the conversion of CO<sub>2</sub>. The synergistic effects of combining ILs with porous materials in CO<sub>2</sub> conversion are thoroughly discussed. Furthermore, an in‐depth analysis is provided regarding the potential prospects and future applications of utilizing ILs‐functionalized porous materials within the broader realm of catalytic CO<sub>2</sub> conversion technologies.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400316"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142227009","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":"Diastereoselective Synthesis of Meso‐1,2‐Diarylethane‐1,2‐Diamines Via Sodium Reduction of Imidazolines","authors":"Daniil R. Bazanov , Natalia A. Lozinskaya","doi":"10.1002/ajoc.202400305","DOIUrl":"10.1002/ajoc.202400305","url":null,"abstract":"<div><div>A facile method for the preparation of meso‐1,2‐diarylethane‐1,2‐diamines from aromatic aldehydes is disclosed. The stereoselectivity of the protocol is based on the disrotatory electrocyclic ring closure of readily generated diazopentadienes, followed by a SET reduction of the imidazoline fragment by sodium. The method is readily scalable to multi‐gram quantities and a wide range of alkoxy and alkyl‐phenyl substituents can be synthesized.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400305"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141784140","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":"Non‐Electronic Activation of Anthracenes Using Steric Repulsion of the 9‐Substituent with Chloro Groups at the peri‐Positions","authors":"Annisa Indah Reza , Kento Iwai , Nagatoshi Nishiwaki","doi":"10.1002/ajoc.202400381","DOIUrl":"10.1002/ajoc.202400381","url":null,"abstract":"<div><div>We investigated how the introduction of substituent at the 9‐ or 10‐position of the 1,8‐dichloroanthracene framework affects the horizontal and vertical distortions of the anthracene rings. The 9‐substituted anthracenes showed higher distortions than their 10‐substituted counterparts due to the steric repulsion with two chloro groups at the <em>peri</em>‐positions. The distortion of anthracene framework affected their reactivity. Indeed, 9‐substituted anthracenes exhibited higher reactivity to undergo the Diels–Alder reaction with maleic anhydride, which was a result of non‐electronic activation.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400381"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217022","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}
Dr. Isabella F. S. Marra , Ms. Larissa P. Silva , Dr. Pedro P. De Castro , Dr. Leonã S. Flores , Dr. Kleber T. De Oliveira , Dr. Paulo E. N. De Souza , Dr. Brenno A. D. Neto , Dr. Hélio F. Dos Santos , Dr. Giovanni W. Amarante
{"title":"Visible‐Light‐Enabled Dual‐Catalysis Approach to Stereoselective [2+2] Cycloaddition of Erlenmeyer‐Plöchl Azlactones","authors":"Dr. Isabella F. S. Marra , Ms. Larissa P. Silva , Dr. Pedro P. De Castro , Dr. Leonã S. Flores , Dr. Kleber T. De Oliveira , Dr. Paulo E. N. De Souza , Dr. Brenno A. D. Neto , Dr. Hélio F. Dos Santos , Dr. Giovanni W. Amarante","doi":"10.1002/ajoc.202400271","DOIUrl":"10.1002/ajoc.202400271","url":null,"abstract":"<div><div>Visible‐light‐driven dual catalysis was employed to stereoselectively produce densely substituted cyclobutanes from Erlenmeyer‐Plöchl azlactones. The single‐step preparation of non‐natural amino acid dimers containing the cyclobutane moiety was achieved through a synergy between iridium photocatalysis and catalytic nickel(II) triflate as a Lewis acid. The desired 1,2‐(<em>zeta</em>)‐<em>Z</em>,<em>E</em>‐isomers were isolated in good yields and with high regio‐ and diastereoselectivity (in all cases, >19 : 1 d.r.). To the best of our knowledge, this is the first report of direct access to truxinic acid analogues using azlactones. Control experiments, EPR reaction monitoring, and DFT calculations suggest that the presence of a Lewis acid, combined with the use of powerful blue LEDs, plays a crucial role in the reactivity of this reaction.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400271"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217024","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}
Dr. Jiahao Liu , Jiachun Nie , Prof. Dr. Zhe Wang , Prof. Dr. Terumasa Kato , Prof. Dr. Yan Liu , Prof. Dr. Keiji Maruoka
{"title":"Facile Generation of Trideuteromethyl Radical from Alkylsilyl Peroxide and Subsequent Functionalization","authors":"Dr. Jiahao Liu , Jiachun Nie , Prof. Dr. Zhe Wang , Prof. Dr. Terumasa Kato , Prof. Dr. Yan Liu , Prof. Dr. Keiji Maruoka","doi":"10.1002/ajoc.202400382","DOIUrl":"10.1002/ajoc.202400382","url":null,"abstract":"<div><div>Cu‐ and Fe‐ catalyzed trideuteromethylation reactions using alkylsilyl peroxide as trideuteromethyl radical precursor are reported. The alkylsilyl peroxide was synthesized from acetone‐d6 in a three‐step sequence, and the reactions with various coupling partners afforded efficiently the corresponding N−CD<sub>3</sub>, O−CD<sub>3</sub> and C−CD<sub>3</sub> bond formation products. The radical heptadeuteriopropylation using alkylsilyl peroxide prepared from butyric acid‐d7 is also described.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400382"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217021","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}
Omkar Bains , Ashish Kumar , Raj Kamal , Ravinder Kumar , Rajesh Kumar , Tanmay Rom , Avijit Kumar Paul
{"title":"Facile and Metal‐Free Synthesis of Isoflavones Using α‐Aryl‐β,β‐Ditosyloxy Ketones","authors":"Omkar Bains , Ashish Kumar , Raj Kamal , Ravinder Kumar , Rajesh Kumar , Tanmay Rom , Avijit Kumar Paul","doi":"10.1002/ajoc.202400336","DOIUrl":"10.1002/ajoc.202400336","url":null,"abstract":"<div><div>Considering the drawbacks associated with available synthetic methodologies of isoflavones, herein we have reported a metal‐free and eco‐friendly approach to these natural products. In the present study, we have carried out the synthesis of eight isoflavone derivatives <strong>7a</strong>–<strong>7h</strong> using α‐aryl‐β,β‐ditosyloxy ketone protocol. Initially, we have protected the 2’‐hydroxy group of respective chalcone moiety in order to remove its interference under reaction conditions. The protected chalcones were then subjected to 1,2‐aryl migration by being treated with hydroxy(tosyloxy)iodobenzene (HTIB) reagent in a non‐nucleophilic solvent (CH<sub>2</sub>Cl<sub>2</sub>). This migration furnished the formation of α‐aryl‐β,β‐ditosyloxy ketones via C−C bond formation from their corresponding chalcones in moderate to good yields (55–82 %). The ambiguity regarding the exact molecular structure of the α‐aryl‐β,β‐ditosyloxy ketones was examined through the single crystal X‐ray diffraction data. At last, the synthesis of isoflavones was carried out in moderate to good yields (50–80 %) by performing the reaction of α‐aryl‐β,β‐ditosyloxy ketones with sodium hydroxide in aqueous methanol.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400336"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217017","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}
Tianyang Zhang , Xianfu Fang , Xin Wang , Huicong Wang , Gong Zhang , Wei Fang , Yangfeng Li , Yizhou Li
{"title":"DNA‐Compatible Nitriles Hydrolysis for Late‐Stage Functionalization of DNA‐Encoded Libraries","authors":"Tianyang Zhang , Xianfu Fang , Xin Wang , Huicong Wang , Gong Zhang , Wei Fang , Yangfeng Li , Yizhou Li","doi":"10.1002/ajoc.202400280","DOIUrl":"10.1002/ajoc.202400280","url":null,"abstract":"<div><div>Primary amides play a crucial role in organic and pharmaceutical synthesis. Herein, we present a rapid and convenient method for transforming diverse DNA‐conjugated nitriles into primary amides utilizing hydrogen peroxide and potassium carbonate. The substrate scope and DEL compatibility of this reaction were thoroughly investigated, revealing a wide range of substrates with moderate‐to‐excellent conversion. This on‐DNA transformation holds significant promise for constructing DNA‐encoded libraries (DELs) and enabling late‐stage functionalization to expand chemical diversity. Our approach not only highlights the versatility of the method but also underscores its potential for broad applications in organic and pharmaceutical synthesis.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400280"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217020","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":"Silane‐Mediated Alkylation of Arenes via Reductive Friedel‐Crafts Reaction Using Carbonyl Compounds","authors":"Jabir Khan , Rina Mahato , Kanhaiya , Chinmoy Kumar Hazra","doi":"10.1002/ajoc.202400347","DOIUrl":"10.1002/ajoc.202400347","url":null,"abstract":"<div><div>A metal‐free one‐pot synthesis route has been documented for the production of 1,1‐unsymmetrical di‐aryl alkanes <em>via</em> reductive Friedel−Crafts alkylation of arenes with carbonyl compounds in 1,1,1,3,3,3,–hexafluoroisopropanol (HFIP) solvent. This approach exhibits a wide substrate scope accommodating diverse functionalities. The transformation of carbonyl compounds into alkylated products is facilitated by dimethylchlorosilane (Me<sub>2</sub>SiClH) reduction, succeeded <em>via</em> nucleophilic attack of arenes. The established protocol demonstrates a promising strategy for converting indoline‐2,3‐dione into <em>α</em>‐aryl oxindoles with high yields. The reaction involves reduction with Me<sub>2</sub>SiClH, followed by the attack of arenes in the presence of a TfOH catalyst. The devised protocol offers scalability and remarkable tolerance towards various functional groups. Control experiments provide insights into the reaction mechanism, highlighting the crucial roles of HFIP and Me<sub>2</sub>SiClH. Furthermore, the method is adaptable for late‐stage functionalization of numerous natural products and pharmaceuticals such as Sesamol, Thymol, Paracetamol, Menthol, and Nerol. Significantly, the technique has proven effective in efficiently synthesising the anticoagulant drug Phenprocoumon and the rodent control agent Coumatetralyl.</div></div>","PeriodicalId":130,"journal":{"name":"Asian Journal of Organic Chemistry","volume":"13 11","pages":"Article e202400347"},"PeriodicalIF":2.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217025","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}