西尾英倫君が中心となって行った金ナノ粒子と固体酸の協同触媒反応によるアルキルエステルのC(sp3)–O結合の低温でのボリル化反応に関する研究成果がJournal of the American Chemical Society誌 (ACS)にAcceptされました。Our paper reporting low-temperature borylation of C(sp3)–O bonds of alkyl ethers by cooperative catalysis of gold nanoparticles and solid acids in Journal of the American Chemical Society (ACS).

西尾英倫君が中心となって行った金ナノ粒子と固体酸の協同触媒反応によるアルキルエステルのC(sp³)–O結合の低温でのボリル化反応に関する研究成果がJournal of the American Chemical Society誌 (ACS)にAcceptされました。Our paper reporting low-temperature borylation of C(sp³)–O bonds of alkyl ethers by cooperative catalysis of gold nanoparticles and solid acids in Journal of the American Chemical Society (ACS).

「Low-Temperature Borylation of C(sp³)–O Bonds of Alkyl Ethers by Gold–Metal Oxide Cooperative Catalysis」.

HIdenori Nishio, Hiroki Miura, and Tetsuya Shishido

Journal of the American Chemical Society, 146, 50, 34690–34701. DOI: 10.1021/jacs.4c13003

 

Since ether moieties are often found not only in petrochemical products but also in natural organic molecules, the development of methods for manipulating C–O bonds of ethers is important for expanding the range of compound libraries synthesized from biomass resources, which should contribute to the goal of carbon neutrality. We report herein that gold nanoparticles supported on Lewis acidic metal oxides, namely α-Fe₂O₃, showed excellent catalytic activity for the reaction of dialkyl ethers and diborons, which enables the conversion of unactivated C(sp³)–O bonds to C(sp³)–B bonds at around room temperature. Various acyclic and cyclic ethers as well as a series of diborons participated in the heterogeneous gold-catalyzed borylation of unactivated C(sp³)–O bonds, to give a series of alkylboronates in high yields. Mechanistic studies corroborated that the present borylation of C(sp³)–O bonds of dialkyl ethers proceeded at the interface between gold nanoparticles and Lewis acidic metal oxides. Furthermore, adsorption IR measurements supported the notion that strong Lewis acid sites were generated at the boron atom of diborons adsorbed at the interface between Lewis acidic metal oxides and gold nanoparticles, which enabled us to ensure that the cooperation of gold nanoparticles and Lewis acidic metal oxides was responsible for the efficient transformation of unactivated C(sp³)–O bonds in ethers under mild conditions. This novel reaction technology which is specific to heterogeneous catalysts enables the activation of stable C(sp³)–O bonds of oxygenated chemical feedstock, which is beneficial for the sustainable synthesis of value-added organoboron compounds.