DEVELOPMENT AND APPLICATION OF VARIOUS KNOEVENAGEL α,γ-DIFUNCTIONALIZATION METHODOLOGIES

Primali V. Navaratne, Alexander J. Grenning

Department of Chemistry, University of Florida, Gainesville FL32611-7200

We are investigating, developing and applying Knoevenagel adducts as a platform for multifunctionalization and complex molecular synthesis. Initial results revealed that Knoevenagel adducts can act as trimethylenemethane (TMM) dipole surrogates where intermolecular α,γ-difunctionalization is possible. Along with that, a route to 1-aryl tetralin lignans by Knoevenagel adducts via deconjugative α-alkylation/intramolecular 6-endo-trig Heck cyclization was developed. This demonstrated the intramolecular version of α,γ-difunctionalization. Recent advancement on α,γ-difunctionalization of Knoevenagel adducts include a simple, tunable synthetic plan to convene an array of galiellactone and analogues, utilizing deconjugative α-alkylation/decarboxylative-Saegusa oxidation methodology.