Jinbao Wu, Yuichiro Kadonaga, Benke Hong, Jin Wang, Xiaoguang Lei*
Angew. Chem. Int. Ed. 2019, 58, 10879-10883
A concise and enantioselective total synthesis of (+)‐jungermatrobrunin A (1), possessing a unique bicyclo[3.2.1]octene ring skeleton with an unprecedented peroxide bridge, was accomplished in 13 steps via a visible light mediated late‐stage Schenck ene reaction of (‐)‐1α,6α‐diacetoxyjungermannenone C (2). Along the way, a striking UV light induced bicyclo[3.2.1]octene ring rearrangement was applied to afford (+)‐12‐hydroxy‐1α,6α‐diacetoxy‐ent‐kaura‐9(11),16‐dien‐15‐one (4). The photoinduced divergent skeletal rearrangements strongly suggest a possible biogenetic relationship between 1, 2 and 4
A concise and enantioselective total synthesis of (+)‐jungermatrobrunin A (1), possessing a unique bicyclo[3.2.1]octene ring skeleton with an unprecedented peroxide bridge, was accomplished in 13 steps via a visible light mediated late‐stage Schenck ene reaction of (‐)‐1α,6α‐diacetoxyjungermannenone C (2). Along the way, a striking UV light induced bicyclo[3.2.1]octene ring rearrangement was applied to afford (+)‐12‐hydroxy‐1α,6α‐diacetoxy‐ent‐kaura‐9(11),16‐dien‐15‐one (4). The photoinduced divergent skeletal rearrangements strongly suggest a possible biogenetic relationship between 1, 2 and 4