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Formation of Ruthenium Carbenes by gem ‐Hydrogen Transfer to Internal Alkynes: Implications for Alkyne trans ‐Hydrogenation
Author(s) -
Leutzsch Markus,
Wolf Larry M.,
Gupta Puneet,
Fuchs Michael,
Thiel Walter,
Farès Christophe,
Fürstner Alois
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201506075
Subject(s) - alkyne , carbene , ruthenium , alkene , chemistry , geminal , photochemistry , transfer hydrogenation , nuclear magnetic resonance spectroscopy , dehydrogenation , catalysis , medicinal chemistry , stereochemistry , organic chemistry
Insights into the mechanism of the unusual trans ‐hydrogenation of internal alkynes catalyzed by {Cp*Ru} complexes were gained by para‐hydrogen (p‐H 2 ) induced polarization (PHIP) transfer NMR spectroscopy. It was found that the productive trans ‐reduction competes with a pathway in which both H atoms of H 2 are delivered to a single alkyne C atom of the substrate while the second alkyne C atom is converted into a metal carbene. This “ geminal hydrogenation” mode seems unprecedented; it was independently confirmed by the isolation and structural characterization of a ruthenium carbene complex stabilized by secondary inter‐ligand interactions. A detailed DFT study shows that the trans alkene and the carbene complex originate from a common metallacyclopropene intermediate. Furthermore, the computational analysis and the PHIP NMR data concur in that the metal carbene is the major gateway to olefin isomerization and over‐reduction, which frequently interfere with regular alkyne trans ‐hydrogenation.