Herein, a computational investigation of the Lewis acid (LA)-catalyzed Diels–Alder (DA) reaction involving \(\hbox {CO}_{2}\) as the dienophile and furan as the diene is presented. Density functional theory (DFT) calculations have been conducted at the B3LYP-D3(BJ)/TZ2P level, utilizing several Lewis acids (LAs) as catalyst models, including \(\hbox {AlCl}_{3}\) , \(\hbox {ZnCl}_{2}\) , \(\hbox {BF}_{3}\) , and \(\hbox {I}_{2}\) . By comparing the DA catalyzed and uncatalyzed pathways, it was possible to identify LA as significantly impacting the reaction mechanism of the DA reaction involving the \(\hbox {CO}_{2}\) , producing stable reaction intermediates, and influencing the DA reaction barriers. DFT calculations indicate that \(\hbox {AlCl}_{3}\) emerges as the most promising catalyst for \(\hbox {CO}_{2}\) utilization, promoting the DA adduct with lower reaction barriers compared with the other LAs investigated. We further investigated the origin of LA’s catalytic influence by combining the activation strain model (ASM) and energy decomposition analysis (EDA). \(\hbox {AlCl}_{3}\) provides the best picture of the balance between structural distortion and electronic interaction with \(\hbox {CO}_{2}\) . Specifically, \(\hbox {AlCl}_{3}\) promotes the strongest orbital interactions and most favorable electrostatic interactions involving the LA- \(\hbox {CO}_{2}\) fragments in the DA transition states.
