Bulky magnesium(ii) and sodium(i) bisphenoxide catalysts for chemoselective transesterification of methyl (meth)acrylates

Xue Zhao; Manussada Ratanasak; Kazumasa Kon; Jun-Ya Hasegawa; Kazuaki Ishihara

doi:10.1039/d2sc05413b

Bulky magnesium(ii) and sodium(i) bisphenoxide catalysts for chemoselective transesterification of methyl (meth)acrylates

Chem Sci. 2022 Nov 28;14(3):566-572. doi: 10.1039/d2sc05413b. eCollection 2023 Jan 18.

Authors

Xue Zhao¹, Manussada Ratanasak², Kazumasa Kon^{1

3}, Jun-Ya Hasegawa², Kazuaki Ishihara³

Affiliations

¹ Graduate School of Engineering, Nagoya University B2-3(611) Furo-cho, Chikusa Nagoya 464-8603 Japan ishihara@cc.nagoya-u.ac.jp.
² Section of Theoretical Catalytic Chemistry, Institute for Catalysis, Hokkaido University Sapporo Hokkaido 011-0021 Japan hesegawa@cat.hokudai.ac.jp.
³ Venture Business Laboratory, Nagoya University B2-4 Furo-cho, Chikusa Nagoya 464-0814 Japan.

Abstract

Given the industrial importance of (meth)acrylate esters, various groups have devoted considerable effort to investigating their chemoselective transesterification. In 2021, we developed magnesium(ii) and sodium(i) complexes derived from 2,6-di-tert-butyl-p-cresol (BHT-H) as chemoselective catalysts for the transesterification of methyl acrylate (MA) and methyl methacrylate (MMA), respectively. Based on our results, we report the discovery of magnesium(ii) and sodium(i) salts derived from 6,6'-(propane-2,2'-diyl)bis(2,4-di-tert-butylphenol) (PBTP-H₂), i.e. Mg(PBTP) and Na₂(PBTP), which are 41 and 81 times more effective catalysts than Mg(BHT)₂ and Na(BHT) for the transesterification of MA and MMA, respectively. These new catalysts are highly effective across an extensive range of alcohols, including primary and secondary alcohols, diols, and triols. Overall, this efficient transesterification technology can be expected to find practical applications in industrial process chemistry.