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  trans-Hydrogenation, gem-Hydrogenation, and trans-Hydrometalation of Alkynes: An Interim Report on an Unorthodox Reactivity Paradigm

Fürstner, A. (2019). trans-Hydrogenation, gem-Hydrogenation, and trans-Hydrometalation of Alkynes: An Interim Report on an Unorthodox Reactivity Paradigm. Journal of the American Chemical Society, 141(1), 11-24. doi:10.1021/jacs.8b09782.

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 Creators:
Fürstner, Alois1, Author           
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1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              

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 Abstract: cis-Delivery of H2 to the π-system of an unsaturated substrate is the canonical course of metal catalyzed hydrogenation reactions. The semireduction of internal alkynes with the aid of [Cp*Ru]-based catalysts violates this rule and affords E-alkenes by direct trans-hydrogenation. A pathway involving σ-complexes and metallacyclopropenes accounts for this unconventional outcome. Connected to this process is an even more striking reactivity mode, in which both H atoms of H2 are delivered to one and the same C atom. Such gem-hydrogenation of stable carbogenic compunds is a fundamentally new transformation that leads to the formation of discrete metal carbene complexes. Computational studies suggest that the trans- and the gem-pathway have similar barriers, but polar substituents in the vicinity of the reacting triple bond provide opportunities for imposing selectivity and control. Moreover, it is shown that catalytic trans-hydrogenation is by no means a singularity: rather, the underlying principle is also manifest in trans-hydroboration, trans-hydrosilylation, trans-hydrogermylation, and trans-hydrostannation, which are equally paradigm-changing processes. These reactions are robust and distinguished by excellent compatibility with many (reducible) functional groups and have already stood the test of natural product synthesis in a number of demanding cases.

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Language(s): eng - English
 Dates: 2018-09-102918-11-132019-01-09
 Publication Status: Published in print
 Pages: 14
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.8b09782
 Degree: -

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Title: Journal of the American Chemical Society
  Other : J. Am. Chem. Soc.
  Abbreviation : JACS
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 141 (1) Sequence Number: - Start / End Page: 11 - 24 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870