Dirhodium(ii)-catalyzed ortho C-H amination of sterically congested N,N-dialkylanilinesElectronic supplementary information (ESI) available: Detailed experimental procedures, spectral data, X-ray crystallographic data for 2g. CCDC 1828111. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8ob01974f

Dirhodium( ii )-catalyzed ortho C-H amination of N , N -dialkylanilines has been developed. Sterically congested 1,2-diaminobenzenes were obtained in high yields with excellent chemo- and regioselectivities from para -substituted anilines and even from para -unsubstituted anilines. The ortho selectivity observed was rationalized in terms of the interaction between the dialkylamino group and a Rh( ii )-nitrene intermediate. Rhodium( ii )-catalyzed C-H amination of N , N -dialkylanilines proceeded in excellent ortho selectivities regardless of whether the para position was substituted or not.