We report a rhodium(II)-catalyzed highly enantioselective 1,3-dipolar cycloaddition reaction between the carbonyl moiety of tropone and carbonyl ylides to afford troponoids in good to high yields with excellent enantioselectivity. We demonstrate that α-diazoketone-derived carbonyl ylides, in contrast to carbonyl ylides derived from diazodiketoesters, undergo [6+3] cycloaddition reactions with tropone to yield the corresponding bridged heterocycles with excellent stereoselectivity. Decisive dipoles: In the rhodium(II)-catalyzed asymmetric 1,3-dipolar cycloaddition of tropone with carbonyl ylides, a programmable chemoselective reaction with the keto group or the 6 π system of tropone was controlled by the substrate (see scheme). The developed method enables the synthesis of complex products in highly enantiomerically enriched form. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.