Synthetic Strategies to Diverse Polyquinanes via Olefin Metathesis: Access to the Basic Core of Crinipellin, Presilphiperfolanol, and Cucumin

A rapid and useful synthetic approach to various polyquinane-based natural products was accomplished efficiently by employing ring-rearrangement metathesis and ring-closing metathesis as key steps. Here, we report the synthesis of stereochemically well-defined cis-anti-cis triquinanes (1, 2), tetraquinanes (3, 4), a novel pentaquinane 5, and fused [5-5-5-6] tetracyclic systems (6, 7) that are present in crinipellin, presilphiperfolanol, cucumin, etc. Hence, the current strategy may be suitable for the synthesis of various complex natural and unnatural cyclopentanoid targets. Moreover, our approach to the newly synthesized pentaquinane 5 has paved the way for various complex polyquinanes/molecules having significant applications in theoretical and medicinal chemistry.