Alejandro Rey, Dr. Andrés Arribas, Prof. Dr. José L. Mascareñas, Dr. Fernando López
{"title":"配体激活的化学和区域选择性Ir(I)催化的烯类分子间碳酸化反应:获得具有全碳四元中心的支链产物","authors":"Alejandro Rey, Dr. Andrés Arribas, Prof. Dr. José L. Mascareñas, Dr. Fernando López","doi":"10.1002/ange.202512027","DOIUrl":null,"url":null,"abstract":"<p>An iridium complex featuring the perfluorinated bisphosphine ligand d<sup>F</sup>ppe can catalyze intermolecular hydrocarbonation reactions of allenes with precise control over the selectivity to yield highly valuable branched products instead of the more common linear derivatives. Using <i>N</i>-substituted 3-carboxamide pyrroles as C─H donors, the reaction gives exclusively C-4 substituted products, while furan analogues yield C-2 substituted derivatives. β-Unsubstituted acrylamides can also be used as C─H sources to give chiral skipped dienes. The additions are equally efficient using monosubstituted and 1,1-disubstituted allenes, enabling the efficient formation of products bearing tertiary and all-carbon quaternary stereocenters. Moreover, a preliminary analysis with chiral bisphosphinite ligands confirms the feasibility of an enantioselective variant. Computational (DFT) studies provide relevant insights into this remarkable ligand-driven branched selectivity.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 40","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202512027","citationCount":"0","resultStr":"{\"title\":\"Ligand-Enabled Chemo- and Regioselective Ir(I)-Catalyzed Intermolecular Hydrocarbonation of Allenes: Access to Branched Products with All-Carbon Quaternary Centers\",\"authors\":\"Alejandro Rey, Dr. Andrés Arribas, Prof. Dr. José L. Mascareñas, Dr. Fernando López\",\"doi\":\"10.1002/ange.202512027\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>An iridium complex featuring the perfluorinated bisphosphine ligand d<sup>F</sup>ppe can catalyze intermolecular hydrocarbonation reactions of allenes with precise control over the selectivity to yield highly valuable branched products instead of the more common linear derivatives. Using <i>N</i>-substituted 3-carboxamide pyrroles as C─H donors, the reaction gives exclusively C-4 substituted products, while furan analogues yield C-2 substituted derivatives. β-Unsubstituted acrylamides can also be used as C─H sources to give chiral skipped dienes. The additions are equally efficient using monosubstituted and 1,1-disubstituted allenes, enabling the efficient formation of products bearing tertiary and all-carbon quaternary stereocenters. Moreover, a preliminary analysis with chiral bisphosphinite ligands confirms the feasibility of an enantioselective variant. Computational (DFT) studies provide relevant insights into this remarkable ligand-driven branched selectivity.</p>\",\"PeriodicalId\":7803,\"journal\":{\"name\":\"Angewandte Chemie\",\"volume\":\"137 40\",\"pages\":\"\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2025-08-22\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202512027\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Angewandte Chemie\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/ange.202512027\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie","FirstCategoryId":"1085","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/ange.202512027","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Ligand-Enabled Chemo- and Regioselective Ir(I)-Catalyzed Intermolecular Hydrocarbonation of Allenes: Access to Branched Products with All-Carbon Quaternary Centers
An iridium complex featuring the perfluorinated bisphosphine ligand dFppe can catalyze intermolecular hydrocarbonation reactions of allenes with precise control over the selectivity to yield highly valuable branched products instead of the more common linear derivatives. Using N-substituted 3-carboxamide pyrroles as C─H donors, the reaction gives exclusively C-4 substituted products, while furan analogues yield C-2 substituted derivatives. β-Unsubstituted acrylamides can also be used as C─H sources to give chiral skipped dienes. The additions are equally efficient using monosubstituted and 1,1-disubstituted allenes, enabling the efficient formation of products bearing tertiary and all-carbon quaternary stereocenters. Moreover, a preliminary analysis with chiral bisphosphinite ligands confirms the feasibility of an enantioselective variant. Computational (DFT) studies provide relevant insights into this remarkable ligand-driven branched selectivity.