Unveiling the importance of catalyst framework and non covalent interactions in an asymmetric Fe-catalyzed O-H insertion: insights from computational tools.

Fe-based catalysts as well as enzymes typically yield low stereoselectivity for carbene insertion into X-H bonds. Here, we have utilized DFT methods to understand the mechanism and unusually high enantioselectivity in an Fe-spiroBox catalyzed carbene insertion reaction into the O-H bond of aliphatic alcohols. Our transition state model shows a unique binding of the reaction intermediates to the chiral catalyst enabled by weak non covalent interactions that is absent in other X-H insertion reactions.