Competitive stereochemical control operative during conrotatory electrocyclization of helically equilibrating diquinanyl-substituted 1,3,5,7-octatetraenyl bisenolates.

[Carbohydrate structure: see text] Activation of the squarate ester cascade by adding the lithiated bicyclo[3.3.0]octene 20 and vinyllithium sequentially to 1 results in the isolation of the four tetracyclic products 21-24. The structures of the topographically complex products were deduced by 2D NMR spectroscopy and X-ray diffraction studies. The mechanistic insights gained by these findings are discussed. The product distribution is telltale evidence for predominant 1,2-addition of the second alkenyl anion. Product stereochemistry is in turn diagnostic of the preferred mode of conrotatory ring closure operating within equilibrating helical intermediates of opposite pitch. A competing pathway for the elimination of methanol in these highly functionalized intermediates has been observed for the first time.