Synthesis and Diels–Alder Reactivity of Substituted [4]Dendralenes

• DOI: 10.1021/acs.joc.5b02583
• Publication Date: 2016-01-12T22:06:57Z
• Authors: Mehmet F. Saglam; Ali R. Alborzi; Alan D. Payne; Anthony C. Willis; Michael N. Paddon...; Michael S. Sherburn
• Keywords: Diels–Alder reaction; Reactivity

The first synthesis of all five possible monomethylated [4]dendralenes has been achieved via two distinct synthetic strategies. Diels-Alder chemistry these new dendralenes (as multidienes) with an electron poor dienophile, N-methylmaleimide (NMM), studied. Thus, simply upon mixing the dendralene and excess dienophile at ambient temperature in a common solvent, sequences cycloadditions result rapid generation complex multicyclic products. Distinct product distributions are obtained differently substituted dendralenes, demonstrating that substitution influences pathway followed, when matrix mechanistic possibilities exists. Dendralene site selectivities traced to electronic, steric conformational effects, thereby allowing predictive tools for applications future endeavors.