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通过光驱动的内炔烃偕氢化实现的格拉布斯复分解反应

Grubbs Metathesis Enabled by a Light-Driven gem-Hydrogenation of Internal Alkynes.

作者信息

Biberger Tobias, Zachmann Raphael J, Fürstner Alois

机构信息

Max-Planck-Institut für Kohlenforschung, 45470, Mülheim/Ruhr, Germany.

出版信息

Angew Chem Int Ed Engl. 2020 Oct 12;59(42):18423-18429. doi: 10.1002/anie.202007030. Epub 2020 Aug 20.

DOI:10.1002/anie.202007030
PMID:32608043
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7589215/
Abstract

[(NHC)(cymene)RuCl ] (NHC=N-heterocyclic carbene) complexes instigate a light-driven gem-hydrogenation of internal alkynes with concomitant formation of discrete Grubbs-type ruthenium carbene species. This unorthodox reactivity mode is harnessed in the form of a "hydrogenative metathesis" reaction, which converts an enyne substrate into a cyclic alkene. The intervention of ruthenium carbenes formed in the actual gem-hydrogenation step was proven by the isolation and crystallographic characterization of a rather unusual representative of this series carrying an unconfined alkyl group on a disubstituted carbene center.

摘要

[(NHC)(对异丙基苯)钌氯合物]（NHC = N-杂环卡宾）配合物引发内炔烃的光驱动偕氢化反应，并伴随形成离散的格拉布型钌卡宾物种。这种非传统的反应模式以“氢化复分解”反应的形式得到应用，该反应将烯炔底物转化为环状烯烃。通过分离和晶体学表征该系列中一个相当不寻常的代表物（其在二取代卡宾中心带有一个无限制的烷基），证明了在实际偕氢化步骤中形成的钌卡宾的介入。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/98a2923c2752/ANIE-59-18423-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/02a3be6a7821/ANIE-59-18423-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/0596f6c6d4d8/ANIE-59-18423-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/b3ac005bb6e2/ANIE-59-18423-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/ea016e04d220/ANIE-59-18423-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/d4c077688c3a/ANIE-59-18423-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/31871baa02d6/ANIE-59-18423-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/98a2923c2752/ANIE-59-18423-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/02a3be6a7821/ANIE-59-18423-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/0596f6c6d4d8/ANIE-59-18423-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/b3ac005bb6e2/ANIE-59-18423-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/ea016e04d220/ANIE-59-18423-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/d4c077688c3a/ANIE-59-18423-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/31871baa02d6/ANIE-59-18423-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f081/7589215/98a2923c2752/ANIE-59-18423-g007.jpg

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Hydrogenative Cyclopropanation and Hydrogenative Metathesis.
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