Diverse Alkyl-Silyl Cross-Coupling via Homolysis of Unactivated C(sp3)-O Bonds with the Cooperation of Gold Nanoparticles and Amphoteric Zirconium Oxides

Hiroki Miura; Masafumi Doi; Yuki Yasui; Yosuke Masaki; Hidenori Nishio; Tetsuya Shishido

doi:10.1021/jacs.2c12311

Diverse Alkyl-Silyl Cross-Coupling via Homolysis of Unactivated C(sp³)-O Bonds with the Cooperation of Gold Nanoparticles and Amphoteric Zirconium Oxides

J Am Chem Soc. 2023 Mar 1;145(8):4613-4625. doi: 10.1021/jacs.2c12311. Epub 2023 Feb 20.

Authors

Hiroki Miura^{1

2

3}, Masafumi Doi¹, Yuki Yasui¹, Yosuke Masaki¹, Hidenori Nishio¹, Tetsuya Shishido^{1

2

3}

Affiliations

¹ Department of Applied Chemistry for Environment, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo 192-0397, Japan.
² Research Center for Hydrogen Energy-Based Society, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo 192-0397, Japan.
³ Elements Strategy Initiative for Catalysts & Batteries, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8520, Japan.

PMID: 36802588
DOI: 10.1021/jacs.2c12311

Abstract

Since C(sp³)-O bonds are a ubiquitous chemical motif in both natural and artificial organic molecules, the universal transformation of C(sp³)-O bonds will be a key technology for achieving carbon neutrality. We report herein that gold nanoparticles supported on amphoteric metal oxides, namely, ZrO₂, efficiently generated alkyl radicals via homolysis of unactivated C(sp³)-O bonds, which consequently promoted C(sp³)-Si bond formation to give diverse organosilicon compounds. A wide array of esters and ethers, which are either commercially available or easily synthesized from alcohols participated in the heterogeneous gold-catalyzed silylation by disilanes to give diverse alkyl-, allyl-, benzyl-, and allenyl silanes in high yields. In addition, this novel reaction technology for C(sp³)-O bond transformation could be applied to the upcycling of polyesters, i.e., the degradation of polyesters and the synthesis of organosilanes were realized concurrently by the unique catalysis of supported gold nanoparticles. Mechanistic studies corroborated the notion that the generation of alkyl radicals is involved in C(sp³)-Si coupling and the cooperation of gold and an acid-base pair on ZrO₂ is responsible for the homolysis of stable C(sp³)-O bonds. The high reusability and air tolerance of the heterogeneous gold catalysts as well as a simple, scalable, and green reaction system enabled the practical synthesis of diverse organosilicon compounds.