Synthesis of the core structure of apicularen a by transannular cyclization.
[reaction: see text] An approach to the macrocyclic core of apicularen A is described. Thus, cross-coupling of the aryl triflate 7 with the vinylstannane 19 provided the styrene 20. Deprotection led to the dihydroxy acid 22. Through a size-selective macrolactonization, the 12-membered macrolactone 23 was obtained. Treatment of 24 with N-phenyl selenophthalimide gave the desired trans-pyran 24. This approach might parallel the biosynthetic pathway.
Kühnert
Sven M
SM
Institut für Organische Chemie, Universität Tübingen, Auf der Morgenstelle 18, D-72076 Tübingen, Germany.
Maier
Martin E
ME
D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis*; D003500:Cyclization; D004791:Enzyme Inhibitors / Q000138:chemical synthesis*; D007202:Indicators and Reagents; D008958:Models, Molecular; D008968:Molecular Conformation; D006180:Proton-Translocating ATPases / Q000037:antagonists & inhibitors*
D019086:Bridged Bicyclo Compounds, Heterocyclic; D004791:Enzyme Inhibitors; D007202:Indicators and Reagents; C117813:apicularen A; D006180:Proton-Translocating ATPases