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Suzuki-Miyaura cross-coupling reaction catalyzed by [R3Si-IPr]Pd complexes: a computational study

Toru Matsui 1
Toru Matsui
, 
Jun Fujiwara 1
Jun Fujiwara
, 
Norihisa Fukaya 2
Norihisa Fukaya
, 
1 Department of Chemistry, University of Tsukuba, Tsukuba, Jupan
2 National Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki, Japan
10.1016/j.mencom.2024.01.011
Published 2023-12-25
Communication , Volume 34, Issue 1, 34-38
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Matsui T. et al. Suzuki-Miyaura cross-coupling reaction catalyzed by [R3Si-IPr]Pd complexes: a computational study // Mendeleev Communications. 2023. Vol. 34. No. 1. pp. 34-38.
GOST all authors (up to 50) Copy
Matsui T., Fujiwara J., Fukaya N., Lee V. Y. Suzuki-Miyaura cross-coupling reaction catalyzed by [R3Si-IPr]Pd complexes: a computational study // Mendeleev Communications. 2023. Vol. 34. No. 1. pp. 34-38.
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TY - JOUR
DO - 10.1016/j.mencom.2024.01.011
UR - https://mendcomm.colab.ws/publications/10.1016/j.mencom.2024.01.011
TI - Suzuki-Miyaura cross-coupling reaction catalyzed by [R3Si-IPr]Pd complexes: a computational study
T2 - Mendeleev Communications
AU - Matsui, Toru
AU - Fujiwara, Jun
AU - Fukaya, Norihisa
AU - Lee, Vladimir Yaroslavovich
PY - 2023
DA - 2023/12/25
PB - Mendeleev Communications
SP - 34-38
IS - 1
VL - 34
ER -
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@article{2023_Matsui,
author = {Toru Matsui and Jun Fujiwara and Norihisa Fukaya and Vladimir Yaroslavovich Lee},
title = {Suzuki-Miyaura cross-coupling reaction catalyzed by [R3Si-IPr]Pd complexes: a computational study},
journal = {Mendeleev Communications},
year = {2023},
volume = {34},
publisher = {Mendeleev Communications},
month = {Dec},
url = {https://mendcomm.colab.ws/publications/10.1016/j.mencom.2024.01.011},
number = {1},
pages = {34--38},
doi = {10.1016/j.mencom.2024.01.011}
}
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Matsui, Toru, et al. “Suzuki-Miyaura cross-coupling reaction catalyzed by [R3Si-IPr]Pd complexes: a computational study.” Mendeleev Communications, vol. 34, no. 1, Dec. 2023, pp. 34-38. https://mendcomm.colab.ws/publications/10.1016/j.mencom.2024.01.011.
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Keywords

catalytic cycle
cross-coupling.
DFT calculations
oxidative addition
reductive elimination
Suzuki–Miyaura reaction
transmetalation

Abstract

The cross-coupling reaction of chlorobenzene and phenylboronic acid, catalyzed by the [R3Si-IPr]Pd0 species (generated upon activation of {[R3Si-IPr]Pd(η3-allyl)Cl} pre-catalyst complexes) in the presence of hydroxide ion as a base, was studied in details by the quantum chemical calculations. Each step of the whole process, including pre-catalyst activation, oxidative addition, transmetalation and reductive elimination, were computationally probed to locate reaction intermediates and transition states along the reaction coordinate. Accordingly, transmetalation was found to be a limiting step of the catalytic cycle (involving oxidative addition, transmetalation and reductive elimination), whereas pre-catalyst activation was revealed as a limiting step of the whole catalytic process.

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