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Synthesis 1995; 1995(9): 1081-1088
DOI: 10.1055/s-1995-4077
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A Stereospecific Transannular Diels-Alder Approach to the [6.6.7] Tricyclic Skeleton Related to Aphidicolin and Scopadulan Natural Products

Dennis G. Hall, Alain-Sébastien Caillé, Marc Drouin, Serge Lamothe, Renate Müller, Pierre Deslongchamps*
  • *Laboratoire de synthèse organique, Département de chimie, Faculté des sciences, Université de Sherbrooke, Sherbrooke, Québec J1K 2R1, Canada, Fax +1(819)8217910; E-mail dlnchamp@structure.chimie.usherb.ca
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Publication Date:
31 December 2000 (online)

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Model trans-cis-cis (TCC) macrocyclic triene 7 was synthesized using a convergent approach. Upon heating at 200°C, a 1,5-hydrogen-shift on the diene moiety was found to compete with the transannular Diels-Alder (TADA) reaction, thus leading to a mixture of tricyclic products. However, the diene rearrangement could be avoided by using boron trifluoride-diethyl ether complex as catalyst at reduced temperature (60°C). The exclusive formation of the trans-syn-cis [6.6.7] (TSC) tricyclic product 8 through an endo approach was observed. This result demonstrates the feasibility of a TADA strategy for synthesizing the title compounds and analogs.

transannular cycloaddition - Diels-Alder reaction - trans-cis diene - Lewis acid catalysis - trans-syn-cis [6.6.7] skeleton