Highly Selective Diels−Alder Reactions of Dienophiles with 1,3-Cyclohexadiene Mediated by Yb(OTf)3·2H2O and Ultrahigh Pressures

Abstract
Ultrahigh pressures and catalytic Yb(OTf)3·2H2O were found to mediate Diels−Alder reactions of various electron-deficient dienophiles with 1,3-cyclohexadiene to produce endo-bicyclo[2.2.2]oct-2-enes in moderate to excellent yield and selectivity. The proposed total synthesis of hapalindole Q based on bicyclo[2.2.2]oct-2-ene construction by Diels−Alder reaction and subsequent olefin cleavage is outlined. Preliminary results demonstrating the viability of this strategy are presented.

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