Synthetic studies toward maoecrystal V are reported. An oxidative dearomatization/Diels-Alder cascade to assemble the natural product carbocyclic core in one step is proposed. A facile electrocyclization is shown to suppress the intramolecular allene Diels-Alder pathway. This obstacle is alleviated via a stepwise approach with an allene equivalent to access the key cyclopentadiene-fused [2.2.2]-bicyclic core. Upon treatment with Lewis acid, the proposed intramolecular hetero- Diels-Alder reaction is cleanly and unexpectedly diverted either via C-C bond-forming fragmentation to the spiro-indene product (when R = OMe) or via elimination (when R = H).
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry