Highly Regio- and Enantioselective Dienylation of p-Quinone Methides Enabled by an Organocatalyzed Isomerization/Addition Cascade of Allenoates

A novel catalytic asymmetric dienylation of para-quinone methides with allenoates has been developed. Under mild conditions catalyzed by ( R)-SITCP, various dienylated bisarylmethides were obtained in moderate to good yields (up to 82% yield) and excellent enantioselectivities (90-98% ees). The efficacy and robustness were demonstrated by 27 examples of chiral dienylation products. A plausible mechanism, which involved 1,2 H-shift and umpolung of allenoates, was proposed based on deuterium labeling experiments and previous reports.