beta(2)-Amino carbonyls, an alpha-substituted beta-amino scaffold, hold a prominent place in the development of new pharmaceuticals and peptidomimetics. Herein, we report a highly efficient Rh-catalyzed ring-opening amidation of substituted cyclopropanols, which turned out to serve as a linchpin for the selective synthesis of beta(2)-amino ketones to outcompete the formation of beta(3)-isomers. Instead of the generally accepted rationale to consider steric factors for the beta(2)-selectivity, orbital interaction was elucidated to play a more critical role in the amidative ring-opening of cyclopropanols to generate the key Rh-C intermediate. Subsequent inner-sphere acylnitrene transfer was achieved in excellent efficiency (TON > 5000) by using readily accessible dioxazolones as the amino source to afford beta(2)-amino ketones with broad applicability.