Periselectivity, Chemoselectivity, and Regioselectivity of the Cycloaddition Reaction of Aza‐Oxyallyl Cations With Cinnamaldehyde: A Density Functional Theory Study

ABSTRACT This study theoretically investigates the factors controlling the periselectivity, chemoselectivity, and regioselectivity of the [3 + 2] cycloaddition reaction of aza‐oxyallyl cation with cinnamaldehyde to form oxazolidinone. The research utilizes hybrid density functional theory (DFT) method at the B3LYP‐D3, B3LYP, M06, and M062X coupled with the 6‐311G (d, p) level of theories to explain that the [3 + 2] chemoselective addition of aza‐oxyallyl cation across the carbonyl bond of cinnamaldehyde through its C and N reactive sites is more favorable than any other plausible mechanism. Generally, electron‐donating groups (EDGs) on aza‐oxyallyl cation decrease the activation barriers, whereas electron‐withdrawing groups (EWGs) increase the activation barrier. The GEDT values predict a very low polar reaction for the [3 + 2] cycloaddition reaction.