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oai:figshare.com:article/34032654 2026-09-30T13:36:23Z category_4 category_8 category_12 category_13 category_14 category_24 category_873 category_39 category_62 category_69 category_132 portal_63 item_type_6 month_year_09_2026

Divergent Synthesis of Heterocycles through Cascade Rearrangements of Dienyne-Amides and Dialkyl Bromomalonates Mengwei You (23949184) Yongli Li (527489) Sisi Huang (760857) Jiahong Wu (12222819) Lei Shen (76320) Hui Mao (115181) Liejin Zhou (7817726) Tianli Wang (1438498) Biochemistry Microbiology Cell Biology Genetics Molecular Biology Evolutionary Biology Chemical Sciences not elsewhere classified Ecology Marine Biology Inorganic Chemistry Infectious Diseases whereas heating triggers vinyl cyclopropane rearrangement structurally diverse molecules enabling selective access broad substrate scope 3 ]- rearrangement cope rearrangement cascade controlled cascade rearrangement three distinct n silver catalysis redirects controlled skeletal rearrangements room temperature promotes divergent heterocycle synthesis afford spirocyclic heterocycles cascade rearrangements divergent synthesis gold catalysis distinct class protocol features oxotriene formation high selectivity high diastereoselectivity heterocyclic scaffolds fused dihydroazepines furnish furan dialkyl bromomalonates common precursors Divergent synthesis provides efficient access to structurally diverse molecules from common precursors. Herein, we report a catalyst- and temperature-controlled cascade rearrangement of dienyne-amides with dialkyl bromomalonates, enabling selective access to three distinct N,O-heterocyclic scaffolds. Gold catalysis at room temperature promotes the cycloisomerization/cyclopropanation/1-aza-Cope rearrangement cascade to furnish furan-fused dihydroazepines, whereas heating triggers a formal [1,3]-rearrangement to afford spirocyclic heterocycles with high diastereoselectivity. Alternatively, silver catalysis redirects the reaction through oxotriene formation and vinyl cyclopropane rearrangement, providing a distinct class of spirocycles. This protocol features a broad substrate scope, high selectivity, and scalability, highlighting the utility of controlled skeletal rearrangements for divergent heterocycle synthesis. 2026-09-30T00:00:00Z Text Journal contribution 10.1021/acs.orglett.6c03702.s001 https://figshare.com/articles/journal_contribution/Divergent_Synthesis_of_Heterocycles_through_Cascade_Rearrangements_of_Dienyne-Amides_and_Dialkyl_Bromomalonates/34032654 CC BY-NC 4.0