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The rhodium(III)‐catalyzed cross‐coupling reaction between N‐sulfonyl aldimines and various olefins such as maleimides, fumarates, maleates, α,β‐unsaturated ketones, acrylate and nitroalkenes is described. This transformation efficiently leads to the diastereoselective synthesis of pharmacologically privileged 1‐aminoindane derivatives via the C−H alkylation followed by subsequent intramolecular cyclization. Notably, single diastereomers in all cases were observed, and the relative stereochemistry of products was confirmed by the X‐ray crystallographic data.