Cyclopropanation Using Electrons Derived from Hydrogen: Reaction of Alkenes and Hydrogen without Hydrogenation

Seiji Ogo; Takeshi Yatabe; Keishi Miyazawa; Yunosuke Hashimoto; Chiaki Takahashi; Hidetaka Nakai; Yoshihito Shiota

doi:10.1021/jacsau.4c00098

Cyclopropanation Using Electrons Derived from Hydrogen: Reaction of Alkenes and Hydrogen without Hydrogenation

JACS Au. 2024 Mar 25;4(4):1615-1622. doi: 10.1021/jacsau.4c00098. eCollection 2024 Apr 22.

Authors

Seiji Ogo^{1

2

3}, Takeshi Yatabe^{1

2

3}, Keishi Miyazawa^{1

2}, Yunosuke Hashimoto^{1

2}, Chiaki Takahashi^{1

2}, Hidetaka Nakai⁴, Yoshihito Shiota⁵

Affiliations

¹ Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
² International Institute for Carbon-Neutral Energy Research (WPI Academy I2CNER), Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
³ Center for Small Molecule Energy, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.
⁴ Department of Energy and Materials, Faculty of Science and Engineering, Kindai University, 3-4-1 Kowakae, Osaka 577-8502, Japan.
⁵ Institute for Materials Chemistry and Engineering, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, Japan.

Abstract

Have you ever imagined reactions of alkenes with hydrogen that result in anything other than hydrogenation or hydrogenative C-C coupling? We have long sought to develop not only hydrogenation catalysts that activate H₂ as hydride ions but also electron transfer catalysts that activate H₂ as a direct electron donor. Here, we report the reductive cyclopropanation of alkenes using an iridium electron storage catalyst with H₂ as the electron source without releasing metal waste from the reductant. We discuss the catalytic mechanism with selectivity to give the trans-isomer. These findings are based on the isolation of three complexes and density functional theory calculations.