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

The first enantioselective synthesis of the reported structure of taiwaniadduct F (2) has been accomplished in a highly regioselective manner through a biomimetic intermolecular [5+2] cycloaddition under extremely mild conditions where trans-ozic acid methyl ester (4a) serves as the dipolarophile and a p-benzoquinone of abeo-abietane (20) 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.