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X-ray analysis of the derivative of 6i unambiguously established its structure having a tetracyclic structure containing the bicyclo[4.1.0]heptene skeleton (see the Supporting Information for details).
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The relative configurations of 12 and 15 were determined based on the NOE experiments (see the Supporting Information for details).
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In the cases of 14a and 14b, the cyclobutene derivatives with Z-alkene moiety were not obtained at all. However, negligible amounts of the cyclobutene derivatives with the E-alkene moiety (13 and the n-pentyl analogue of 13) were detected.
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The optical resolution of (±)-5c by HPLC provided (+)-5c (99% ee) and (-)-5c (99% ee), both of which were independently reacted under standard reaction conditions to produce (-)-6c (99% ee) and (+)-6c (99% ee), respectively, in quantitative yields. The absolute configurations of these four compounds have not yet been determined, but these two experiments unambiguously provided additional evidence that this ring-closing reaction must proceed in a stereospecific fashion.
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