Catalytic Asymmetric Total Synthesis of (−)-Garryine via an Enantioselective Heck Reaction

Abstract

The first asymmetric total synthesis of the hexacyclic veatchine-type C 20 -diterpenoid alkaloid (−)-garryine is presented. Key steps include a Pd-catalyzed enantioselective Heck reaction, a radical cyclization, and a photoinduced C−H activation/oxazolidine formation sequence. Of note, a highly enantioselective Heck reaction developed in this work provides efficient access to 6/6/6 tricyclic compounds, in particular, containing a C19-functionalitiy, which is useful for diverse transformations.

Total Synthesis of (±)-Simonsol C

“…Figure illustrates that the common tetrahydrodibenzo­[b,d]­furan motif is crucial for achieving total synthesis, which is a primary focus of our research . This subunit can be accessed using an intramolecular Heck reaction and dearomatization under basic conditions . However, reports on the synthesis of natural products featuring quaternary carbons substituted with allyl and aryl groups are still limited.…”