Song Yu

Vrije Universiteit Amsterdam | VU · Department of Chemistry and Pharmaceutical Sciences

We have quantum chemically studied the base‐catalyzed Diels‐Alder (DA) reaction between 3hydroxy‐2‐pyrone and N‐methylmaleimide using dispersion‐corrected density functional theory. The uncatalyzed reaction is slow and is preceded by the extrusion of CO2 via a retro‐DA reaction. Base catalysis, e.g., by triethylamine, lowers the reaction barrier up...

Brønsted acid‐catalyzed inverse‐electron demand (IED) aza‐Diels‐Alder reactions between 2‐aza‐dienes and ethylene were studied using quantum chemical calculations. The computed activation energy systematically decreases as the basic sites of the diene progressively become protonated. Our activation strain and Kohn‐Sham molecular orbital analyses tr...

External electric fields can be used to control the reactivity and selectivity of chemical reactions. Using state‐of‐the‐art quantum chemical computations, this work provides a desperately needed causal model to explain how judiciously oriented external electric fields catalyze and steer the stereoselectivity of the Diels–Alder reactions. These res...

A judiciously oriented external electric field (OEEF) can catalyze a wide range of reactions and can even induce endo/exo stereoselectivity of cycloaddition reactions. We study the Diels-Alder reaction between cyclopentadiene and maleic anhydride using quantitative activation strain and Kohn-Sham molecular orbital theory to pinpoint the origin of t...

We have quantum chemically studied the reactivity, site‐, and regioselectivity of the 1,3‐dipolar cycloaddition reaction between methyl azide and various allenes, including the archetypal allene propadiene, heteroallenes, and cyclic allenes, using density functional theory (DFT). The 1,3‐dipolar cycloaddition reactivity of linear (hetero)allenes de...

Recently, attention on the pyridine adsorption and reaction at the electrode/electrolyte interface have been revitalized in the context of pyridine-mediated reactions such as CO2 reduction. Taking Pt as an example, although numerous efforts have been made, disagreements are still unresolved for the potential-dependent adsorption of pyridine on the...

We have quantum chemically explored the Diels–Alder reactivities of a systematic series of hetero‐1,3‐butadienes with ethylene by using density functional theory at the BP86/TZ2P level. Activation strain analyses provided physical insight into the factors controlling the relative cycloaddition reactivity of aza‐ and oxa‐1,3‐butadienes. We find that...

Electrocatalytic CO2 reduction to CO emerges as a potential route of utilizing the excessively emitted CO2. Metal‐N‐C hybrid structures have shown unique activities, of which the active centers and reaction mechanisms, however, remain unclear due to the ambiguity in true atomic structures for prepared catalysts. Herein, combining density functional...

Electrocatalytic CO2 reduction to CO emerges as a potential route of utilizing the excessively emitted CO2. Metal‐N‐C hybrid structures have shown unique activities, of which the active centers and reaction mechanisms, however, remain unclear due to the ambiguity in true atomic structures for prepared catalysts. Herein, combining density functional...

This report describes a density functional theory investigation into the reactivities of a series of aza‐1,3‐dipoles with ethylene at the BP86/TZ2P level. A benchmark study was carried out using QMflows, a newly developed program for automated workflows of quantum chemical calculations. In total, 24 1,3‐dipolar cycloaddition (1,3‐DCA) reactions wer...

Rational design and construction of local environment of active sites on noble metal surfaces are a promising but challenging approach for developing high-selectivity catalysts. Here, we present an effective approach via engineering local active sites, aiming to solve the critical problem of H2S and CO poisoning of Pt catalysts for H2 electrooxidat...