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Updated: Aug 6, 2026

Preparation of a Corannulene-functionalized Hexahelicene by Copper(I)-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
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Cyclobutenone-Based Syntheses of Polyquinanes and Bicyclo[6.3.0]undecanes by Tandem Anionic Oxy-Cope Reactions. Total
James M. MacDougall1, Vincent J. Santora, Sharad K. Verma
1Department of Chemistry, University of California, Irvine, California 92697-2025.
Abstract:
The addition of ethenyllithium derivatives to the carbonyl of dialkyl squarate-derived bicycloheptenones, e.g., 1a and 6a, initiates a low-temperature anion-accelerated oxy-Cope rearrangement to provide polyquinanes by a transannular aldol reaction of the intermediate bicyclo[6.3.0]undecadienone 4. Additional functionality is introduced by alkylation of the enolate 3 resulting from the oxy-Cope rearrangement. Phosphorylation or triflation of enolate 3 provides an entry into the bicyclo[6.3.0]undecane ring system. An application of this new methodology is demonstrated by the total synthesis of the sesquiterpene natural product (+/-)-precapnelladiene from diisopropyl squarate (10 steps, 12%).
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