Selective Copper Complex-Catalyzed Hydrodefluorination of Fluoroalkenes and Allyl Fluorides: A Tale of Two Mechanisms

The transition to more economically friendly small-chain fluorinated groups is leading to a resurgence in the synthesis and reactivity of fluoroalkenes. One versatile method to obtain a variety of commercially relevant hydrofluoroalkenes involves the catalytic hydrodefluorination (HDF) of fluoroalke...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2019-07, Vol.141 (29), p.11506-11521
Main Authors: Andrella, Nicholas O, Xu, Nancy, Gabidullin, Bulat M, Ehm, Christian, Baker, R. Tom
Format: Article
Language:English
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Summary:The transition to more economically friendly small-chain fluorinated groups is leading to a resurgence in the synthesis and reactivity of fluoroalkenes. One versatile method to obtain a variety of commercially relevant hydrofluoroalkenes involves the catalytic hydrodefluorination (HDF) of fluoroalkenes using silanes. In this work it is shown that copper hydride complexes of tertiary phosphorus ligands (L) can be tuned to achieve selective multiple HDF of fluoroalkenes. In one example, HDF of the hexafluoropropene dimer affords a single isomer of heptafluoro-2-methylpentene in which five fluorines have been selectively replaced with hydrogens. DFT computational studies suggest a distinct HDF mechanisms for L2CuH (bidentate or bulky monodentate phosphines) and L3CuH (small cone angle monodentate phosphines) catalysts, allowing for stereocontrol of the HDF of trifluoroethylene.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.9b03101