Structural Chemistry of C–N Axially Chiral Compounds

In the last several years, atropisomers owing to the rotational restriction around a C-N single bond (C-N axially chiral compounds) have attracted significant attention in the field of synthetic organic chemistry. In particular, the highly enantioselective synthesis of various C-N axially chiral compounds and their application to asymmetric reactions have been reported by many groups. On the other hand, studies on the structural chemistry of C-N axially chiral compounds have attracted scant attention in comparison with synthetic studies. For over 25 years, our group has explored asymmetric synthesis of C-N axially chiral compounds and their synthetic application. In the course of these synthetic studies, we found several notable structural properties in relation to the C-N bond rotation and an association of enantiomers (the relationship between the rotational stability and the structure or electronic effect, the chirality-dependent halogen bond, and the self-disproportionation of enantiomers). Furthermore, on the basis of these structural properties, the development of acid-mediated molecular rotors and the synthesis of isotopic atropisomers possessing high stereochemical purity and rotational stability were achieved. Through this Perspective, I wish to make the chemistry community aware that C-N axially chiral compounds are attractive molecules from the viewpoints of both synthetic organic chemistry and structural chemistry.