2,3-Diaryl Indanone Construction via the Neophyl Rearrangement
Zhikun Wu1, Lingzhi Hu1, Shunxi Dong1
1Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China.
Abstract:
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.
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