Mechanistic Studies of the Deslongchamps Annulation

The Cs2CO3-mediated annulations (“Deslongchamps annulations”) of three spirocyclic benzoquinone monoketals 5b–d with an ester or acyl substituent at C-2 to two tert-butyl esters of γ,δ-unsaturated β-ketocarboxyl acids (“Nazarov reagents”; 2a,b) were monitored 1H NMR spectroscopically. This revealed that a primary product, by all likelihood the Michael adduct, forms fast and prior to the appearance of the Deslongchamps adduct. These primary products form reversibly. This was proved by two crossover and four scavenging experiments. Therein, components already incorporated in one of the mentioned primary products ended up in Deslongchamps adducts different from the one, which would have resulted if the respective primary product had reacted alone. However, these experiments leave open whether our primary products are intermediates en route to Deslongchamps products or whether they represent dead ends.