Catalytic C–O Bond Cleavage of Vinyl Ethers via Dehydrovinylation and Tandem Tishchenko Coupling
4 affiliations
- 1Department of Chemistry and Chemical Biology
- 2Rutgers The State University of New Jersey, New Brunswick
- 3Department of Chemistry
- 4Rutgers University–Camden
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.
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BibTeX
@misc{parihar2026catalytic,
title = {{Catalytic C–O Bond Cleavage of Vinyl Ethers via Dehydrovinylation and Tandem Tishchenko Coupling}},
author = {Ashish Parihar and Soham Chakraborty and Santanu Malakar and Alan S. Goldman},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010232/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010232/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Catalytic C–O Bond Cleavage of Vinyl Ethers via Dehydrovinylation and Tandem Tishchenko Coupling
AU - Ashish Parihar
AU - Soham Chakraborty
AU - Santanu Malakar
AU - Alan S. Goldman
PY - 2026
DA - 2026/10/11
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010232/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010232/v1
AB - 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.
ER -