Marta Velázquez, Pilar Elías-Rodríguez, Tomás Tejero, Rosario Fernández*, Pedro Merino*, José M. Lassaletta* and David Monge*,
{"title":"利用硫脲-氯超分子配合物中的非共价π型相互作用:重氮杂环的不对称脱芳化","authors":"Marta Velázquez, Pilar Elías-Rodríguez, Tomás Tejero, Rosario Fernández*, Pedro Merino*, José M. Lassaletta* and David Monge*, ","doi":"10.1021/acscatal.5c04438","DOIUrl":null,"url":null,"abstract":"<p >Enantioselective dearomatization of diazaheterocycles through anion-binding catalysis has been developed. The process involves the nucleophilic addition of phosphorus nucleophiles to <i>in situ</i> generated <i>N</i>-benzoyliminium chlorides, using a <i>tert</i>-leucine-derived thiourea as an H-bond donor catalyst, thereby providing access to appealing cyclic hydrazino phosphonates and their derivatives. Mechanistic investigations suggest that the low solubility of these salts might favor the formation of a supramolecular thiourea–chloride–iminium 2:1:1 complex, which is proposed as the catalytically relevant species accounting for the observed nonlinear effect. Experimental and computational data support a 4H-activation model via this highly ordered ion pair, in which two thiourea molecules are arranged in an antiparallel orientation around the chloride, generating a <i>C</i><sub>2</sub>-symmetric groove. Hence, stereodefined insertion of the <i>N</i>-benzoyliminium is ensured by key noncovalent π-type interactions, thereby maximizing the enantioinduction event.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 16","pages":"14443–14455"},"PeriodicalIF":13.1000,"publicationDate":"2025-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscatal.5c04438","citationCount":"0","resultStr":"{\"title\":\"Harnessing Noncovalent π-Type Interactions in Thiourea–Chloride Supramolecular Complexes: Toward the Asymmetric Dearomatization of Diazaheterocycles\",\"authors\":\"Marta Velázquez, Pilar Elías-Rodríguez, Tomás Tejero, Rosario Fernández*, Pedro Merino*, José M. Lassaletta* and David Monge*, \",\"doi\":\"10.1021/acscatal.5c04438\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Enantioselective dearomatization of diazaheterocycles through anion-binding catalysis has been developed. The process involves the nucleophilic addition of phosphorus nucleophiles to <i>in situ</i> generated <i>N</i>-benzoyliminium chlorides, using a <i>tert</i>-leucine-derived thiourea as an H-bond donor catalyst, thereby providing access to appealing cyclic hydrazino phosphonates and their derivatives. Mechanistic investigations suggest that the low solubility of these salts might favor the formation of a supramolecular thiourea–chloride–iminium 2:1:1 complex, which is proposed as the catalytically relevant species accounting for the observed nonlinear effect. Experimental and computational data support a 4H-activation model via this highly ordered ion pair, in which two thiourea molecules are arranged in an antiparallel orientation around the chloride, generating a <i>C</i><sub>2</sub>-symmetric groove. Hence, stereodefined insertion of the <i>N</i>-benzoyliminium is ensured by key noncovalent π-type interactions, thereby maximizing the enantioinduction event.</p>\",\"PeriodicalId\":9,\"journal\":{\"name\":\"ACS Catalysis \",\"volume\":\"15 16\",\"pages\":\"14443–14455\"},\"PeriodicalIF\":13.1000,\"publicationDate\":\"2025-08-05\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/pdf/10.1021/acscatal.5c04438\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Catalysis \",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acscatal.5c04438\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acscatal.5c04438","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Harnessing Noncovalent π-Type Interactions in Thiourea–Chloride Supramolecular Complexes: Toward the Asymmetric Dearomatization of Diazaheterocycles
Enantioselective dearomatization of diazaheterocycles through anion-binding catalysis has been developed. The process involves the nucleophilic addition of phosphorus nucleophiles to in situ generated N-benzoyliminium chlorides, using a tert-leucine-derived thiourea as an H-bond donor catalyst, thereby providing access to appealing cyclic hydrazino phosphonates and their derivatives. Mechanistic investigations suggest that the low solubility of these salts might favor the formation of a supramolecular thiourea–chloride–iminium 2:1:1 complex, which is proposed as the catalytically relevant species accounting for the observed nonlinear effect. Experimental and computational data support a 4H-activation model via this highly ordered ion pair, in which two thiourea molecules are arranged in an antiparallel orientation around the chloride, generating a C2-symmetric groove. Hence, stereodefined insertion of the N-benzoyliminium is ensured by key noncovalent π-type interactions, thereby maximizing the enantioinduction event.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.