Eduardo García-Padilla, Feliu Maseras* and Antonio M. Echavarren*,
{"title":"金(I)催化的1,6-Enyne单次裂解重排:全貌。","authors":"Eduardo García-Padilla, Feliu Maseras* and Antonio M. Echavarren*, ","doi":"10.1021/acsorginorgau.3c00028","DOIUrl":null,"url":null,"abstract":"<p >We identify the factors that rule the selectivity in single-cleavage skeletal rearrangements promoted by gold(I) catalysts. We find that stereoconvergence is enabled by a rotational equilibrium when electron-rich substituents are used. The anomalous <i>Z-</i>selective skeletal rearrangement is found to be due to electronic factors, whereas <i>endo</i>-selectivity depends on both steric and electronic factors.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":null,"pages":null},"PeriodicalIF":3.3000,"publicationDate":"2023-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/fa/12/gg3c00028.PMC10557124.pdf","citationCount":"0","resultStr":"{\"title\":\"Gold(I)-Catalyzed 1,6-Enyne Single-Cleavage Rearrangements: The Complete Picture\",\"authors\":\"Eduardo García-Padilla, Feliu Maseras* and Antonio M. Echavarren*, \",\"doi\":\"10.1021/acsorginorgau.3c00028\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >We identify the factors that rule the selectivity in single-cleavage skeletal rearrangements promoted by gold(I) catalysts. We find that stereoconvergence is enabled by a rotational equilibrium when electron-rich substituents are used. The anomalous <i>Z-</i>selective skeletal rearrangement is found to be due to electronic factors, whereas <i>endo</i>-selectivity depends on both steric and electronic factors.</p>\",\"PeriodicalId\":29797,\"journal\":{\"name\":\"ACS Organic & Inorganic Au\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2023-08-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://ftp.ncbi.nlm.nih.gov/pub/pmc/oa_pdf/fa/12/gg3c00028.PMC10557124.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Organic & Inorganic Au\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acsorginorgau.3c00028\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Organic & Inorganic Au","FirstCategoryId":"1085","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsorginorgau.3c00028","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Gold(I)-Catalyzed 1,6-Enyne Single-Cleavage Rearrangements: The Complete Picture
We identify the factors that rule the selectivity in single-cleavage skeletal rearrangements promoted by gold(I) catalysts. We find that stereoconvergence is enabled by a rotational equilibrium when electron-rich substituents are used. The anomalous Z-selective skeletal rearrangement is found to be due to electronic factors, whereas endo-selectivity depends on both steric and electronic factors.
期刊介绍:
ACS Organic & Inorganic Au is an open access journal that publishes original experimental and theoretical/computational studies on organic organometallic inorganic crystal growth and engineering and organic process chemistry. Short letters comprehensive articles reviews and perspectives are welcome on topics that include:Organic chemistry Organometallic chemistry Inorganic Chemistry and Organic Process Chemistry.