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

Abstract

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.