Enantioselective Synthesis of Multifunctionalized 4H-Pyrans via Formal [4 + 2] Annulation Process by Bifunctional Phosphonium Salt Catalysis.

Abstract

A highly enantioselective formal [4 + 2] annulation involving electron-deficient allenes as C2-synthons has been developed under bifunctional phosphonium salt catalysis. With this catalytic protocol, a wide range of synthetically interesting and highly functionalized chiral 4H-pyran derivatives were readily prepared in good yields (up to 99%) with outstanding diastereo- and enantioselectivities (up to >20:1 dr, up to >99.9% ee). The utility and the practicality of this method were demonstrated by the gram-scale reaction and facile elaboration. Of note, this is the first example of an asymmetric annulation reaction involving allenic reactants under a phase-transfer catalysis system.