Anastasia A Fesenko, Mikhail S Grigoriev, Anatoly D Shutalev
{"title":"通过不同硫代氨基氮基前驱体的条件控制环三聚化或环二聚化，有效自组装 21 元和 14 元氮杂环。","authors":"Anastasia A Fesenko, Mikhail S Grigoriev, Anatoly D Shutalev","doi":"10.1039/d4ob01384k","DOIUrl":null,"url":null,"abstract":"<p><p>A preparative synthesis of previously unknown 21- and 14-membered azamacrocycles <i>via</i> acid-promoted cyclotrimerization or cyclodimerization of three readily available precursors, namely, 1-amino-6-hydroxy-4,6-dimethylhexahydropyrimidine-2-thione, 4-(4-oxopent-2-yl)thiosemicarbazide hydrazone, and 5,7-dimethyl-1,4,5,6-tetrahydro-3<i>H</i>-1,2,4-triazepine-3-thione has been developed. A dramatic dependence of the selectivity of macrocyclization on the reaction conditions is demonstrated. The thermodynamic aspects of the reactions are discussed based on experimental data and DFT calculation results. Plausible pathways for the formation of macrocycles are proposed.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":null,"pages":null},"PeriodicalIF":4.6000,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Effective self-assembly of 21- and 14-membered azamacrocycles <i>via</i> condition-controlled cyclotrimerization or cyclodimerization of different thiosemicarbazide-based precursors.\",\"authors\":\"Anastasia A Fesenko, Mikhail S Grigoriev, Anatoly D Shutalev\",\"doi\":\"10.1039/d4ob01384k\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>A preparative synthesis of previously unknown 21- and 14-membered azamacrocycles <i>via</i> acid-promoted cyclotrimerization or cyclodimerization of three readily available precursors, namely, 1-amino-6-hydroxy-4,6-dimethylhexahydropyrimidine-2-thione, 4-(4-oxopent-2-yl)thiosemicarbazide hydrazone, and 5,7-dimethyl-1,4,5,6-tetrahydro-3<i>H</i>-1,2,4-triazepine-3-thione has been developed. A dramatic dependence of the selectivity of macrocyclization on the reaction conditions is demonstrated. The thermodynamic aspects of the reactions are discussed based on experimental data and DFT calculation results. Plausible pathways for the formation of macrocycles are proposed.</p>\",\"PeriodicalId\":2,\"journal\":{\"name\":\"ACS Applied Bio Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.6000,\"publicationDate\":\"2024-10-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Applied Bio Materials\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4ob01384k\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"MATERIALS SCIENCE, BIOMATERIALS\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Bio Materials","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4ob01384k","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, BIOMATERIALS","Score":null,"Total":0}
Effective self-assembly of 21- and 14-membered azamacrocycles via condition-controlled cyclotrimerization or cyclodimerization of different thiosemicarbazide-based precursors.
A preparative synthesis of previously unknown 21- and 14-membered azamacrocycles via acid-promoted cyclotrimerization or cyclodimerization of three readily available precursors, namely, 1-amino-6-hydroxy-4,6-dimethylhexahydropyrimidine-2-thione, 4-(4-oxopent-2-yl)thiosemicarbazide hydrazone, and 5,7-dimethyl-1,4,5,6-tetrahydro-3H-1,2,4-triazepine-3-thione has been developed. A dramatic dependence of the selectivity of macrocyclization on the reaction conditions is demonstrated. The thermodynamic aspects of the reactions are discussed based on experimental data and DFT calculation results. Plausible pathways for the formation of macrocycles are proposed.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
