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Accessing rare α-heterocyclic aziridines via Brønsted acid-catalyzed Michael addition/annulation : scope, limitations, and mechanism
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dc.contributor.author | Hilton, Timothy A. | |
dc.contributor.author | Leach, Andrew | |
dc.contributor.author | McKay, Aiden P | |
dc.contributor.author | Watson, Allan J. B. | |
dc.date.accessioned | 2024-02-28T17:30:08Z | |
dc.date.available | 2024-02-28T17:30:08Z | |
dc.date.issued | 2024-02-28 | |
dc.identifier | 299076946 | |
dc.identifier | 1cb72c55-8860-43ce-982e-121e0436280e | |
dc.identifier | 85186206534 | |
dc.identifier.citation | Hilton , T A , Leach , A , McKay , A P & Watson , A J B 2024 , ' Accessing rare α-heterocyclic aziridines via Brønsted acid-catalyzed Michael addition/annulation : scope, limitations, and mechanism ' , Chemistry - A European Journal , vol. Early View , e202303993 . https://doi.org/10.1002/chem.202303993 | en |
dc.identifier.issn | 0947-6539 | |
dc.identifier.other | ORCID: /0000-0002-1582-4286/work/154532627 | |
dc.identifier.uri | https://hdl.handle.net/10023/29379 | |
dc.description | Funding: T.A.H. thanks the University of St Andrews for a PhD studentship. A.J.B.W. thanks the Leverhulme Trust for a Research Fellowship (RF-2022-014). | en |
dc.description.abstract | We report an approach to the diastereoselective synthesis of 1,2-disubstituted heterocyclic aziridines. A Brønsted acid-catalyzed conjugate addition of anilines to trisubstituted heterocyclic chloroalkenes provides an intermediate 1,2-chloroamine. Diastereocontrol was found to vary significantly with solvent selection, with computational modelling confirming selective, spontaneous fragmentation in the presence of trace acids, proceeding through a pseudo-cyclic, protonated intermediate and transition state. These chloroamines can then be converted to the aziridine by treatment with LiHMDS with high stereochemical fidelity. This solvent-induced stereochemical enrichment thereby enables an efficient route to rare cis-aziridines with high dr. The scope, limitations, and mechanistic origins of selectivity are also presented | |
dc.format.extent | 8 | |
dc.format.extent | 10129467 | |
dc.language.iso | eng | |
dc.relation.ispartof | Chemistry - A European Journal | en |
dc.subject | Annulation | en |
dc.subject | Aziridine | en |
dc.subject | Diastereoselectivity | en |
dc.subject | Heterocycles | en |
dc.subject | Mechanism | en |
dc.subject | QD Chemistry | en |
dc.subject | DAS | en |
dc.subject.lcc | QD | en |
dc.title | Accessing rare α-heterocyclic aziridines via Brønsted acid-catalyzed Michael addition/annulation : scope, limitations, and mechanism | en |
dc.type | Journal article | en |
dc.contributor.sponsor | The Leverhulme Trust | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. Sir James Mackenzie Institute for Early Diagnosis | en |
dc.identifier.doi | https://doi.org/10.1002/chem.202303993 | |
dc.description.status | Peer reviewed | en |
dc.identifier.grantnumber | RF-2022-014 | en |
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