Theoretical study of concerted hydroamination‐fragmentation reactions to alkenes and alkynes

Abstract

A new type of concerted cycloaddition-fragmentation reaction utilizing carbamic acid as the amine source is herein reported. This method will require the use of carbamic acid for these reactions that are driven forward by elimination of a highly stable small molecule (CO 2 ). The formation of this gaseous byproducts would make this type of concerted reaction irreversible, driving the reaction to completion. A theoretical study was completed at the B3LYP/6-31G(d,p) level, providing evidence of the feasibility of this reaction. Additional computation work was done to show how adding electron donating groups to carbamic acid and electron withdrawing groups, such as fluorine, to the alkyne can additionally lower the activation energy of this reaction. This potential new methodology of unsaturated systems would allow for hydroaminations without the need for transition metal catalysts.