Formation of ruthenium carbenes by gem-hydrogen transfer to internal alkynes: implications for alkyne trans-hydrogenation.

Angewandte Chemie
Markus LeutzschAlois Fürstner

Abstract

Insights into the mechanism of the unusual trans-hydrogenation of internal alkynes catalyzed by {Cp*Ru} complexes were gained by para-hydrogen (p-H2 ) induced polarization (PHIP) transfer NMR spectroscopy. It was found that the productive trans-reduction competes with a pathway in which both H atoms of H2 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.

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Citations

Oct 7, 2016·Journal of the American Chemical Society·Kenan Tokmic, Alison R Fout
Nov 25, 2016·Chemistry : a European Journal·Heiko Sommer, Alois Fürstner
Oct 13, 2018·Chemical Communications : Chem Comm·Barbara RipkaKerstin Münnemann
Nov 7, 2018·Chemistry : a European Journal·Guillaume MataAlois Fürstner
Nov 14, 2018·Chemistry : a European Journal·Kirill Nikitin, Ryan O'Gara
Apr 30, 2019·Chemical Communications : Chem Comm·Kangkui LiBaomin Fan
Apr 27, 2019·Angewandte Chemie·Sebastian PeilAlois Fürstner
Nov 7, 2019·Chemistry : a European Journal·Niklas O ThielJohannes F Teichert
Feb 8, 2020·Chemistry, an Asian Journal·Dipesh M Sharma, Benudhar Punji
Mar 7, 2020·Chemistry : a European Journal·Damián PadínCarlos Saá
Jun 8, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Wenmin WangJing Ma
May 22, 2018·Chemical Science·Wissam IaliSimon B Duckett
Jun 14, 2019·Chemistry : a European Journal·Lucas W Hernandez, David Sarlah
Jul 2, 2020·Angewandte Chemie·Tobias BibergerAlois Fürstner
Jan 7, 2020·Magnetic Resonance in Medical Sciences : MRMS : an Official Journal of Japan Society of Magnetic Resonance in Medicine·Neil J Stewart, Shingo Matsumoto
Feb 17, 2021·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Neil J StewartShingo Matsumoto
Jul 10, 2021·Chemistry : a European Journal·Romain MelotAlois Fürstner
Feb 9, 2017·Journal of the American Chemical Society·Dragoş-Adrian RoşcaAlois Fürstner
Oct 8, 2019·Journal of the American Chemical Society·Nikolaus GorgasKarl Kirchner
Oct 10, 2019·Journal of the American Chemical Society·Lijuan SongJianwei Sun
Jul 16, 2020·Journal of the American Chemical Society·Qiang FengJianwei Sun
Jan 16, 2018·Journal of the American Chemical Society·Daniel J TindallAlois Fürstner
Feb 13, 2018·Journal of the American Chemical Society·Alexandre GuthertzAlois Fürstner
Sep 15, 2017·Journal of the American Chemical Society·Kenan TokmicAlison R Fout
Feb 7, 2020·The Journal of Organic Chemistry·Andreas EkeberghNina Kann
Aug 14, 2020·Journal of the American Chemical Society·Jieping ChenZhan Lu
Nov 6, 2018·Journal of the American Chemical Society·Hang ShenThomas R Hoye
Oct 20, 2020·Journal of the American Chemical Society·Sebastian PeilAlois Fürstner
Apr 21, 2018·Chemical Reviews·Irina P BeletskayaMiguel Yus

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Methods Mentioned

BETA
NMR

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