Synthesis of Cadinanolide Type of Tricyclic α-Methylene-γ-lactone Using Intramolecular Cyclization of α-Trimethylsilylmethyl-α,β-Unsaturated Ester with Cyclic Ketone

Article abstract of DOI:10.1246/bcsj.69.2297

Fluoride-promoted intramolecular cyclization of ethyl 6-(2-oxocyclohex-1-yl)-2-(trimethylsilylmethyl)hex-2-enoate afforded ethyl 2-(1-hydroxybicyclo[4.4.0]decan-2-yl)acrylate as the major product, together with tricyclic α-methylene-γ-lactone, a model compound of cadinanolides. The former product was also converted to γ-lactone. The cyclization reaction promoted by TiCl₄ gave the hydroxy ester and its dehydrated product. Both Lewis acid- and fluoride-promoted cyclizations gave a trans-decaline system mainly. This stereoselectivity is completely different from that of Reformatsky cyclization observed by Dreiding and co-workers.