Synthesis of 1,n-Diamines via Selective Catalytic C-H Diamination.

Abstract

A new practical strategy for the conversion of alkanes to diamines is reported. It relies on a one-pot dirhodium(II)-catalyzed amination of two C(sp3)-H bonds with sulfamates in the presence of a potent iodine(III) oxidant. This approach gives access to diamines with various substitution patterns depending on the C-H bonds that are cleaved. Thus, it gives access to 1,n-diamines (2 < n < 7) isolated with very high levels of regioselectivity, yields of up to 86%, and enantiomeric ratios of up to 94.5:5.5. The reaction can be performed with two different sulfamates, a process that offers the opportunity to differentiate both nitrogen atoms. The key role of the iodine(III) oxidant for the in situ formation of iminoiodinane is revealed by mass spectrometry experiments.