Unusual KIE and dynamics effects in the Fe-catalyzed hetero-Diels-Alder reaction of unactivated aldehydes and dienes

Yuhong Yang, Xiaoyong Zhang, Li-Ping Zhong, Jialing Lan, Xin Li, Chuang-Chuang Li and Lung Wa Chung ()
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Yuhong Yang: Harbin Institute of Technology
Xiaoyong Zhang: Southern University of Science and Technology
Li-Ping Zhong: Southern University of Science and Technology
Jialing Lan: Harbin Institute of Technology
Xin Li: Southern University of Science and Technology
Chuang-Chuang Li: Southern University of Science and Technology
Lung Wa Chung: Southern University of Science and Technology

Nature Communications, 2020, vol. 11, issue 1, 1-10

Abstract: Abstract Hetero-Diels-Alder (HDA) reaction is an important synthetic method for many natural products. An iron(III) catalyst was developed to catalyze the challenging HDA reaction of unactivated aldehydes and dienes with high selectivity. Here we report extensive density-functional theory (DFT) calculations and molecular dynamics simulations that show effects of iron (including its coordinate mode and/or spin state) on the dynamics of this reaction: considerably enhancing dynamically stepwise process, broadening entrance channel and narrowing exit channel from concerted asynchronous transition states. Also, our combined computational and experimental secondary KIE studies reveal unexpectedly large KIE values for the five-coordinate pathway even with considerable C–C bond forming, due to equilibrium isotope effect from the change in the metal coordination. Moreover, steric and electronic effects are computationally shown to dictate the C=O chemoselectivity for an α,β-unsaturated aldehyde, which is verified experimentally. Our mechanistic study may help design homogeneous, heterogeneous and biological catalysts for this challenging reaction.

Date: 2020
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DOI: 10.1038/s41467-020-15599-w

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