The Total Synthesis of Hyperfirin via a Cyclooctadiene Strategy

Abstract

Polycyclic polyprenylated acylphloroglucinols (PPAPs) combine compelling structural complexity with effective biological activity. The total synthesis of Hyperfirin is reported as one linear sequence. Key to this novel modular strategy is to access the bicyclo[3.3.1]nonane-2,4,9-trione framework via transannular acylation of a decorated eight-membered ring, followed by late stage bridgehead substitution. The described route adds flexibility to PPAP construction and broadens the scope of eight-membered ring chemistry. * sı Supporting InformationThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.orglett.4c01836.Experimental details, characterization data for all new compounds, 1 H and 13 C NMR spectra, and X-ray data information (PDF) FAIR data, including the primary NMR FID files, for compounds 1, 11a,[13][14][15][16]19,[21][22][23][24][25] and 27 (ZIP) Accession Codes CCDC 2353409−2353411 and 2353415 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk