Synthesis of Polycyclic Structures by the Diels−Alder Reaction of Inner-Outer-Ring 1,3-Bis(trimethylsilyloxy)dienesClick to copy article linkArticle link copied!
Abstract

A Diels−Alder reaction of novel inner-outer-ring 1,3-silyloxydienes 5−8 with a variety of dienophiles to afford highly functionalized polycyclic structures is reported. The inner-outer-ring 1,3-silyloxydienes 5−8 containing five- to seven-membered carbocyclic and heterocyclic rings were prepared in a single reaction vessel from 2-acetylcyclocarbonyls in quantitative yields. The Diels−Alder reaction with 1,4-benzoquinone (BQ), dimethyl acetylenedicarboxylate (DMAD), and methyl vinyl ketone (MVK) proceeded smoothly at room temperature, affording functionalized polycyclic naphthols, phenols, and enones with high regioselectivity and good yields (39−75%). Moreover, dienes 5−8 also reacted in a hetero-Diels−Alder reaction with benzaldehyde (BA) and N-benzylideneaniline (NBA) in the presence of catalytic amounts of ZnCl2, affording substituted polycyclic pyranones and pyridinones in good yields (40−93%). Overall, our synthetic strategy provides straightforward access to an interesting set of polycyclic structures useful for natural and nonnatural product synthesis.
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