Lahtigui, OuidadForster, DanDuchemin, CoralieCramer, Nicolai2022-07-182022-07-182022-07-182022-05-1010.1021/acscatal.2c01827https://infoscience.epfl.ch/handle/20.500.14299/189230WOS:000820235100001Rigid saturated nitrogen-containing scaffolds such as 3-azabicyclo[3.1.0]hexanes are very important and frequently occurring motifs in biologically active compounds. We disclose a flexible two-step protocol for their efficient and selective access. A tailored Cp*Rh-III catalyst promotes alkenyl C-H functionalization of N-enoxysuccinimides engaging in rare cis-cyclopropanation of range of primary amines, the dicarbonyl cis-cyclopropanes are efficiently and completely diastereoselectively cyclized by a Cp*Rh-III acrolein to access disubstituted cis-cyclopropanes in high enantio- and diastereoselectivity. Subsequently, in the presence of a broad catalyst via an iterative aminative transfer hydrogen to an exquisite set of substituted 3-azabicyclo[3.1.0]hexanes.Chemistry, PhysicalChemistryasymmetric catalysisc-h functionalizationchiral cp ligandscis-cyclopropanationrhodiumchiral cyclopentadienyl ligandsasymmetric catalysisreductive aminationallylic alcoholscyclopropanationfunctionalizationheterocyclesconstructioncarboxylatesannulationtext::journal::journal article::research article