Zhang, Meng YaoBarrow, Russell2021-12-170022-3263http://hdl.handle.net/1885/256640A nine-step synthesis of boletopsin 11 (1), a bioactive fungal natural product, is disclosed. Key features include a one-pot [O]-oxa-Michael cascade to establish the polyoxygenated dibenzofuran core followed by a Pd-catalyzed directed ortho-C(sp2)–H arylation to complete the fully functionalized carbon skeleton. Exploration of the latter transformation led to the discovery of an unexpected tandem ortho-C(sp2)–H arylation event, and the scope of the directed ortho-C(sp2)–H reaction was further investigated with coupling partners varying in stereoelectronic properties.This study was undertaken with the support of the Research School of Chemistry at the Australian National University and an NHMRC project grant (1028092). M.Y.Z. acknowledges the Australian National University for an Australian Postgraduate Award.application/pdfen-AU© 2018 American Chemical Society201810.1021/acs.joc.8b007922020-11-23