Iterative direct C(sp3)-H functionalization of amines: diastereoselective divergent syntheses of α,α′-disubstituted alicyclic aminesElectronic supplementary information (ESI) available. CCDC 1499395, 952461, 1506220 and 1507198. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6ob02257j

A novel iterative C (sp 3 ) -H oxygenation/C-C bond formation strategy, which avoids repetitive N -protection/-deprotection steps, was developed for direct α,α′-difunctionalization of alicyclic amines. The method is highly efficient and stereoselective in producing syn -α,α′-disubstituted aliphatic N -heterocycles. Synthetic potential and practicability of the method was demonstrated by an easy and straightforward synthesis of neuroactive alkaloid nor -lobelane and its derivatives. Facile access to the syn -α,α′-disubstituted N -heterocycles via iterative C-H oxygenation and C-C bond formation.