Catalytic C–O Bond Cleavage of Vinyl Ethers via Dehydrovinylation and Tandem Tishchenko Coupling
Year: 2026
Type: preprint
Abstract: The cleavage of ether C–O bonds by transition-metal complexes has attracted considerable attention, but catalytic cleavage of vinyl ether C(sp²)–O bonds is largely unexplored. Herein we report the dehydrovinylation of alkyl vinyl ethers catalyzed by a pincer-ligated osmium complex. Primary alkyl vinyl ethers undergo C–O bond cleavage to afford ethylene and the corresponding aldehydes, which undergo tandem Tishchenko coupling to yield esters. Secondary alkyl vinyl ethers undergo dehydrovinylation to afford ethylene and ketones. Experimental observations and density functional theory calculations support a mechanism involving insertion of the vinyl ether C=C bond into an Os–H bond, followed by β-alkoxy elimination and β-hydride elimination to form the carbonyl product. These results establish a new mode of catalytic C(sp²)–O bond cleavage and demonstrate its application in a tandem dehydrovinylation–Tishchenko transformation.
Source: ChemRxiv
Institution: Rutgers, The State University of New Jersey
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7221511216