期刊
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
卷 2021, 期 37, 页码 5275-5283出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejoc.202101107
关键词
Activation strain model; Density functional calculations; Ene reaction; Lewis acids; Reactivity
The study demonstrates that Lewis acid catalysts efficiently accelerate the ene reaction by lowering the reaction barrier and inducing asymmetry in the pi-electronic system, thus relieving activation strain and Pauli repulsion.
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 uncatalyzed reaction. Our detailed activation strain and Kohn-Sham molecular orbital analyses reveal that coordination of a LA catalyst to the enophile decreases the reaction barrier of the ene reaction by inducing an asymmetry in the pi-electronic system, which increases the asynchronicity and hence relieves the otherwise highly destabilizing activation strain and Pauli repulsion between the closed-shell filled pi-orbitals of the ene and enophile. In all, these findings further demonstrate the generality of the Pauli-lowering catalysis concept.
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