The first asymmetric
synthesis of pepluanol A (1)
is presented. The synthesis route is very concise (10 steps) and features
a Curtin–Hammett-driven stereoconvergent intramolecular Diels–Alder
reaction. A Nozaki–Hiyama–Kishi reaction comprises the
connective step, bringing together the seven-membered enone system
bearing the dienophile and the diene in the side chain. Subsequent
stereoconvergent IMDA reaction furnishes the carboskeleton of the
natural product in only 7 steps. The reactions were carried out on
a gram scale up to an advanced intermediate and including the stereoconvergent
intramolecular Diels–Alder reaction.
We report a concise and versatile total synthesis of the diterpenoid (+)‐norcembrene 5 from simple building blocks. Ring‐closing metathesis and an auxiliary‐directed 1,4‐addition are the key steps of our synthetic route. During the synthesis, an unprecedented, highly oxidized pentacyclic structural motif was established from a furanocembranoid through transannular [4+2] cycloaddition.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.