2,3-Diaryl Indanone Construction via the Neophyl Rearrangement

The neophyl rearrangement is a classic radical migration reaction; however, examples that proceed directly from unactivated C(sp³)-H bonds remain rare. We have developed a formal 2,3-difunctionalization of 3,3-disubstituted indanones to construct 2,3-diaryl indanone derivatives, a privileged scaffold in bioactive molecules. The reaction proceeds efficiently using a hypervalent iodine reagent and a catalytic chiral scandium complex with alcohols or water as nucleophiles, delivering products in excellent yields with high diastereoselectivity. Radical generation is rationalized via a sequence of single-electron transfer oxidation and deprotonation by di(acetoxyiodo)benzene, while the alcohol coupling step involves ligand coupling at a novel iodine(III) intermediate.