Eveline H. Tiekink

Vrije Universiteit Amsterdam | VU · Division of Theoretical Chemistry

Tropone is an unreactive diene in normal electron demand Diels- Alder reactions, but it can be activated via carbonyl umpolung by using hydrazone ion analogs. Recently, the higher reactivity of hydrazone ion analogs was ascribed to a raised HOMO energy induced by antiaromaticity (Org. Lett., 2020, 22, 7083). We show that this is incorrect, and that...

The iron‐catalyzed oxidative addition of C(spn)–X bonds (n = 1–3 and X = H, CH3, Cl) in archetypal model substrates H3C–CH2–X, H2C=CH–X and HC≡C–X to Fe(CO)4 was investigated using relativistic density functional theory at ZORA‐OPBE/TZ2P. The C(spn)–X bonds become substantially stronger going from C(sp3)–X to C(sp2)–X to C(sp)–X, whereas the oxidat...

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...

The catalytic effect of various Lewis acids (LAs) on the ene reaction between propene (ene) and but‐3‐en‐2‐one (enophile) was studied quantum chemically using density functional theory and with coupled‐cluster theory. The studied LAs efficiently accelerate the ene reaction by lowering the reaction barrier up to 12 kcal mol–1 compared to the uncatal...

The absolute configuration of a chiral molecule is key to its biological activity. Being able to find out what this configuration is, is thus crucial for a wide range of applications. The difficulties associated with such a determination steeply rise as the number of chiral centers in a given compound becomes larger. Concurrently, it becomes increa...