Intermolecular Hydroalkoxylation of Terminal Alkynes Catalyzed by a Dipyrrinato Rhodium(I) Complex with Unusual Selectivity

An operationally simple and atom-economical method for the E-selective preparation of enol ethers is described. A novel dicarbonyl­(5-phenyldipyrrinato)rhodium complex, 2, was prepared in four synthetic steps, characterized by X-ray crystallography and NMR spectroscopy, and then investigated as a ca...

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Bibliographic Details
Published in:Organometallics 2015-09, Vol.34 (17), p.4312-4317
Main Authors: Lam, Raphael H, Walker, D. Barney, Tucker, Matthew H, Gatus, Mark R. D, Bhadbhade, Mohan, Messerle, Barbara A
Format: Article
Language:English
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Summary:An operationally simple and atom-economical method for the E-selective preparation of enol ethers is described. A novel dicarbonyl­(5-phenyldipyrrinato)rhodium complex, 2, was prepared in four synthetic steps, characterized by X-ray crystallography and NMR spectroscopy, and then investigated as a catalyst for the intermolecular hydroalkoxylation of terminal alkynes. Solvent and substrate studies were used to gain insight into the mechanism of the reaction. Cyclic voltammetry was also used to investigate the electronic properties of 2. The rhodium­(I)-catalyzed intermolecular alkyne hydroalkoxylation reaction reported here mediates excellent substrate transformation with a high degree of E/Z selectivity which is opposite to that reported previously using alternative catalysts.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.5b00561