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

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.

SUBMITTER: Leutzsch M

PROVIDER: S-EPMC4643192 | biostudies-literature | 2015 Oct

REPOSITORIES: biostudies-literature

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

Leutzsch Markus M Wolf Larry M LM Gupta Puneet P Fuchs Michael M Thiel Walter W Farès Christophe C Fürstner Alois A

Angewandte Chemie (International ed. in English) 20150831 42

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 independ ...[more]

PMID: 26332643

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Project description:The only recently discovered gem-hydrogenation of internal alkynes is a fundamentally new transformation, in which both H atoms of dihydrogen are transferred to the same C atom of a triple bond while the other position transforms into a discrete metal carbene complex. [Cp*RuCl]4 is presently the catalyst of choice: the resulting piano-stool ruthenium carbenes can engage a tethered alkene into either cyclopropanation or metathesis, and a prototypical example of such a reactive intermediate with an olefin ligated to the ruthenium center has been isolated and characterized by X-ray diffraction. It is the substitution pattern of the olefin that determines whether metathesis or cyclopropanation takes place: a systematic survey using alkenes of largely different character in combination with a computational study of the mechanism at the local coupled cluster level of theory allowed the preparative results to be sorted and an intuitive model with predictive power to be proposed. This model links the course of the reaction to the polarization of the double bond as well as to the stability of the secondary carbene complex formed, if metathesis were to take place. The first application of "hydrogenative metathesis" to the total synthesis of sinularones E and F concurred with this interpretation and allowed the proposed structure of these marine natural products to be confirmed. During this synthesis, it was found that gem-hydrogenation also provides opportunities for C-H functionalization. Moreover, silylated alkynes are shown to participate well in hydrogenative metathesis, which opens a new entry into valuable allylsilane building blocks. Crystallographic evidence suggests that the polarized [Ru-Cl] bond of the catalyst interacts with the neighboring R3Si group. Since attractive interligand Cl/R3Si contacts had already previously been invoked to explain the outcome of various ruthenium-catalyzed reactions, including trans-hydrosilylation, the experimental confirmation provided herein has implications beyond the present case.

Dataset Information

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

Publications

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

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