Gang Chen , Guangjie Nie , Linxuan Li , Jie Fu , Hui Yao , Nianyu Huang , Nengzhong Wang
{"title":"通过碱催化的化学选择性环化,原子控制的螺旋和融合环的发散合成","authors":"Gang Chen , Guangjie Nie , Linxuan Li , Jie Fu , Hui Yao , Nianyu Huang , Nengzhong Wang","doi":"10.1039/d4qo02400a","DOIUrl":null,"url":null,"abstract":"<div><div>Annulation reactions are recognized for their efficiency in constructing complex cyclic compounds with multiple substitutions, aligning well with green chemistry principles. Herein, we report a transition-metal-free, chemodiverse cycloaddition reaction employing allylamines as [C,N] synthons that react with azadienes in an environmentally benign manner. The protocol has been applied to benzofuran- and indanone-derived azadienes <em>via</em> [3 + 2] cycloadditions, and to benzothiophene-derived azadienes <em>via</em> [3 + 4] cycloadditions, yielding a series of spirobenzofurans, spirotetrandrines, and benzothiophene-diazepines with high diastereoselectivity. In addition to avoiding the use of toxic transition metals, the process demonstrates the potential for further functional group transformations of the cycloaddition products, paving the way for the sustainable generation of valuable intermediates.</div></div>","PeriodicalId":94379,"journal":{"name":"Organic chemistry frontiers : an international journal of organic chemistry","volume":"12 7","pages":"Pages 2212-2218"},"PeriodicalIF":0.0000,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Atom-controlled divergent synthesis of spiro and fused rings via base-catalyzed chemoselective annulation†\",\"authors\":\"Gang Chen , Guangjie Nie , Linxuan Li , Jie Fu , Hui Yao , Nianyu Huang , Nengzhong Wang\",\"doi\":\"10.1039/d4qo02400a\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Annulation reactions are recognized for their efficiency in constructing complex cyclic compounds with multiple substitutions, aligning well with green chemistry principles. Herein, we report a transition-metal-free, chemodiverse cycloaddition reaction employing allylamines as [C,N] synthons that react with azadienes in an environmentally benign manner. The protocol has been applied to benzofuran- and indanone-derived azadienes <em>via</em> [3 + 2] cycloadditions, and to benzothiophene-derived azadienes <em>via</em> [3 + 4] cycloadditions, yielding a series of spirobenzofurans, spirotetrandrines, and benzothiophene-diazepines with high diastereoselectivity. In addition to avoiding the use of toxic transition metals, the process demonstrates the potential for further functional group transformations of the cycloaddition products, paving the way for the sustainable generation of valuable intermediates.</div></div>\",\"PeriodicalId\":94379,\"journal\":{\"name\":\"Organic chemistry frontiers : an international journal of organic chemistry\",\"volume\":\"12 7\",\"pages\":\"Pages 2212-2218\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2025-02-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic chemistry frontiers : an international journal of organic chemistry\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S2052412925000798\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic chemistry frontiers : an international journal of organic chemistry","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S2052412925000798","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Atom-controlled divergent synthesis of spiro and fused rings via base-catalyzed chemoselective annulation†
Annulation reactions are recognized for their efficiency in constructing complex cyclic compounds with multiple substitutions, aligning well with green chemistry principles. Herein, we report a transition-metal-free, chemodiverse cycloaddition reaction employing allylamines as [C,N] synthons that react with azadienes in an environmentally benign manner. The protocol has been applied to benzofuran- and indanone-derived azadienes via [3 + 2] cycloadditions, and to benzothiophene-derived azadienes via [3 + 4] cycloadditions, yielding a series of spirobenzofurans, spirotetrandrines, and benzothiophene-diazepines with high diastereoselectivity. In addition to avoiding the use of toxic transition metals, the process demonstrates the potential for further functional group transformations of the cycloaddition products, paving the way for the sustainable generation of valuable intermediates.