Catalytic aza-Nazarov cyclization reactions to access α-methylene-γ-lactam heterocycles

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dc.authoridDonmez, Selin Ezgi/0000-0002-1377-2689
dc.contributor.authorYagci, Bilge Banu
dc.contributor.authorDonmez, Selin Ezgi
dc.contributor.authorSahin, Onur
dc.contributor.authorTurkmen, Yunus Emre
dc.date.accessioned2025-03-23T19:26:11Z
dc.date.available2025-03-23T19:26:11Z
dc.date.issued2023
dc.departmentSinop Üniversitesi
dc.description.abstractWe have developed a catalytic aza-Nazarov reaction of N-acyliminium salts generated in situ from the reaction of a variety of cyclic and acyclic imines with alpha,13-unsaturated acyl chlorides to afford substituted alpha-methylene-gamma-lactam heterocycles. The reactions proceed effectively in the presence of catalytic (20 mol %) amounts of AgOTf as an anion exchange agent or hydrogen-bond donors such as squaramides and thioureas as anion-binding organocatalysts. The aza-Nazarov cyclization of 3,4-dihydroisoquinolines with alpha,13-unsaturated acyl chlorides gives tricyclic lactam products 7 in up to 79% yield with full diastereocontrol (dr = >99:1). The use of acyclic imines in a similar catalytic aza-Nazarov reaction with 20 mol % of AgOTf results in the formation of alpha-methylene-gamma-lactam heterocycles 19 in up to 76% yield and with good to high diastereoselectivities (4.3:1 to 16:1). We have demonstrated the scalability of the reaction with a gram-scale example. The relative stereochemistry of the alpha-methylene-gamma-lactam products 19 has been determined via the single-crystal X-ray analysis of lactam 19l. In order to shed light on the details of the reaction mechanism, we have performed carefully designed mechanistic studies which consist of experiments on the effect of 13-silicon stabilization, the alkene geometry of the alpha,13-unsaturated acyl chloride reactants, and adventitious water on the success of the catalytic aza-Nazarov reaction.
dc.description.sponsorshipScientific and Technological Research Council of Turkey [116Z171]
dc.description.sponsorshipFinancial support from the Scientific and Technological Research Council of Turkey (TUBITAK; Grant No: 116Z171) is gratefully acknowledged.
dc.identifier.doi10.3762/bjoc.19.6
dc.identifier.endpage77
dc.identifier.issn1860-5397
dc.identifier.pmid36741815
dc.identifier.scopus2-s2.0-85149384421
dc.identifier.scopusqualityQ2
dc.identifier.startpage66
dc.identifier.urihttps://doi.org/10.3762/bjoc.19.6
dc.identifier.urihttps://hdl.handle.net/11486/4652
dc.identifier.volume19
dc.identifier.wosWOS:000921316700001
dc.identifier.wosqualityQ2
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.indekslendigikaynakPubMed
dc.language.isoen
dc.publisherBeilstein-Institut
dc.relation.ispartofBeilstein Journal of Organic Chemistry
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanı
dc.rightsinfo:eu-repo/semantics/openAccess
dc.snmzKA_WOS_20250323
dc.subject?-methylene-?-lactam
dc.subjectaza-Nazarov reaction
dc.subject?-silicon effect
dc.subjectheterocycles
dc.subjectintramolecular cyclization
dc.titleCatalytic aza-Nazarov cyclization reactions to access α-methylene-γ-lactam heterocycles
dc.typeArticle

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