Radical Difunctionalization of Gaseous Ethylene Guided by Quantum Chemical Calculations: Selective Incorporation of Two Molecules of Ethylene

Hideaki Takano; Yong You; Hiroki Hayashi; Yu Harabuchi; Satoshi Maeda; Tsuyoshi Mita

doi:10.1021/acsomega.1c05102

Radical Difunctionalization of Gaseous Ethylene Guided by Quantum Chemical Calculations: Selective Incorporation of Two Molecules of Ethylene

ACS Omega. 2021 Nov 5;6(49):33846-33854. doi: 10.1021/acsomega.1c05102. eCollection 2021 Dec 14.

Authors

Hideaki Takano^{1

2}, Yong You^{1

2}, Hiroki Hayashi^{1

2}, Yu Harabuchi^{1

2

3}, Satoshi Maeda^{1

2

3

4}, Tsuyoshi Mita^{1

2}

Affiliations

¹ Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21, Nishi 10, Kita-ku, Sapporo, Hokkaido 001-0021, Japan.
² JST, ERATO Maeda Artificial Intelligence in Chemical Reaction Design and Discovery Project, Kita 10, Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan.
³ Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10, Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan.
⁴ Research and Services Division of Materials Data and Integrated System (MaDIS), National Institute for Materials Science (NIMS), Tsukuba, Ibaraki 305-0044, Japan.

Abstract

Ethylene, of which about 170 million tons are produced annually worldwide, is a fundamental C₂ feedstock that is widely used on an industrial scale for the synthesis of polyethylenes and polyvinylchlorides. Compared to other alkenes, however, the direct use of ethylene for the synthesis of fine chemicals such as pharmaceuticals and agrochemicals is limited, probably due to its small and gaseous character. We, herein, report a new radical difunctionalization strategy of ethylene, aided by quantum chemical calculations. Computationally proposed imidyl and sulfonyl radicals can be introduced into ethylene in the presence of an Ir photocatalyst under irradiation with blue light-emitting diodes (LEDs) (λ_max = 440 nm). The present reaction systems led to the selective incorporation of two molecules of ethylene into the substrate, which could be rationally explained by computational analysis.