Enantioselective Synthesis of the Proposed Structure of (−)-Taiwaniadduct F

The first enantioselective synthesis of the reported structure of taiwaniadduct F (<b>2</b>) has been accomplished in a highly regioselective manner through a biomimetic intermolecular [5+2] cycloaddition under extremely mild conditions where <i>trans</i>-ozic acid methyl ester (<b>4a</b>) serves as the dipolarophile and a <i>p</i>-benzoquinone of <i>abeo</i>-abietane (<b>20</b>) acts as the 1,5-dipole. In the process, herein, we document the first instance of an oxy-acyloin rearrangement that results in skeleton reassembly of a [6-5-6-5] scaffold into a [6-6-5-6] framework. The absolute configuration was confirmed using X-ray crystallography of advanced intermediates along with detailed 2D NMR analysis.