A highly diastereoselective (5+1) annulation of allenoates and pyrazolones catalyzed by CH3OK

Abstract

The first (5+1) annulation of allenoates and pyrazolones catalyzed by CH₃OK has been reported. A series of spiro-pyrazolone derivatives were obtained as single diastereomers in high yields (≤95%) under mild conditions. The synthetic utility was demonstrated by a scale-up reaction and various transformations of the products. The proposed mechanism suggests that the allenoate works as a 1,5-biselectrophilic 5C synthon for the first time and controlled experiments disclose that K⁺ plays an important role in the diastereoselectivity-determining step through an eight-membered ring transition state. Also, this 1,5-biselectrophilic allenoate will be able to act as a 5C synthon for (5+n) annulation.