Metal-Free Asymmetric Synthesis of Indanes through Chiral Hypervalent Iodine(III)-Mediated Ring Contraction

The iodine­(III)-mediated asymmetric oxidative rearrangement of 1,2-dihydro­naphthalenes was investigated to prepare optically active 1-substituted indanes. The chiral hypervalent iodine species is generated <i>in situ</i> from a chiral aryl iodide, prepared in 94% yield in one step. This metal-free protocol was applied to different cyclic alkenes, substituted with oxygen, with nitrogen, or at position 1 with aryl or methyl. Indanes can be isolated as an acetal or alcohol in up to 78% <i>ee