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

05 September 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

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 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 allenylsilanes 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 polyester 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 amphoteric oxides 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 not only enabled the practical synthesis of diverse organosilicon compounds, but also contributed to the progress toward carbon neutrality.

Keywords

Silylation
Depolymerization
C-O activation
Gold catalyst
Heterogeneous catalyst

Supplementary materials

Title
Description
Actions
Title
Supporting Information
Description
Experimental procedures, characterization of supported Au catalysts, and 1H NMR, 13C NMR of the products
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.