Diastereoselective Diels–Alder Reactions of 1,7,9-Decatrien-3-ones to Highly Substituted Octalin Derivatives

Abstract

Based on an efficient synthesis of 1,7,9-decatrien-3-one precursors we studied their thermal and Lewis acid-promoted intramolecular Diels–Alder reactions to octalin derivatives. Whereas the thermal cycloadditions showed only cis/trans selectivities close to 35:65, the transformations were strongly influenced by the type of Lewis acid employed. With mono-coordinating Lewis acids such as BF₃, cis/trans ratios of up to 85:15 were observed, whereas di-coordinating Lewis acids such as TiCl₂(OiPr)₂ induce fairly high trans-selectivity. This remarkable switch of diastereoselectivity is discussed.

Key words

Diels–Alder reaction - intramolecular cycloaddition - Lewis acid - diastereoselectivity - titanium

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