Effect of Substituents on the Ring-Closing Metathesis Reaction in the Synthesis of Functionalized Nonanolactones

Abstract

The synthesis of functionalized nine-membered ring lactones based on sequential esterification and ring-closing metathesis (RCM) reactions is reported. The effects of olefin substitution and allylic and homoallylic oxygenated substituents on the RCM reaction is analyzed. An unusual cyclization stereochemistry has been observed, leading to a stereoselective olefin formation in the synthesis of nonanolactones. The high selectivity can be rationalized by interaction/coordination of the homoallylic or allylic hydroxyl group with the ruthenium metal center in the ruthenacyclobutane intermediate.

Key words

ring-closing metathesis - nonanolactones - botcinolide - Botrytis cinerea

References and Notes

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13

The geometry of double bond for lactones 19a-c was determined on the basis of NOE experiments. In addition the E-geometry of 19f was assigned by coupling constant between olefinic protons.