10.1002/anie.201810221
Angewandte Chemie International Edition
COMMUNICATION
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Scheme 5. Selected examples of the 1,3-diol formation. d.r. generally 1:1. [a]
Yields determined via 1H-NMR spectroscopic analysis using 1,3,5-
trimethoxybenzene as an internal standard.
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In conclusion, a new orthogonal strategy for COCM has
been developed, which proceeds via the visible-light-
induced hole-catalyzed formation of 1,3-diols and their
acid-induced Grob-type fragmentation. The key advantage
of this strategy is the lower energetic barrier required for
the formation of 1,3-diols relative to oxetanes, which have
previously been used as intermediates for COCM. The
fragmentation of the 1,3-diols provides the cross-
metathesis products with high levels of E-selectivity.
However, this fragmentation, which proceeds via the
formation of carbocation intermediates, also limits this
approach to mostly electron-rich aromatic aldehydes.
Further studies to improve and extend the scope of this
fragmentation step are ongoing in our laboratory. Overall,
this work constitutes a new strategy for the highly desired
carbonyl-olefin cross-metathesis reaction, which we hope
will further aid the development of this field.
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[15] The lower activation barrier for 1,3-diol formation allows for milder
conditions (1,3-diol formation tolerates many functional groups (see
Scheme 5)) and is not the limiting step of this reaction sequence in
contrast to the COM reactions proceeding via oxetanes. The limiting step
here is the Grob fragmentation. We are currently investigating this
fragmentation and hope to provide conditions that improve the scope of
the COCM also to the functional groups present in Scheme 5.
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Acknowledgements
We thank Hyung Yoon, Michael Teders, Felix Klauck, Zackaria
Nairoukh and Michael James for helpful discussions and Tiffany
Paulisch, Matthias Freitag and Max Lübbesmeyer for
experimental support. Generous financial support from the
Deutsche Forschungsgemeinschaft (SFB 858 and Leibniz Award)
and the Fonds der Chemischen Industrie (F.S.) are gratefully
acknowledged.
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[19] For details about the synthesis and characterization of 1 see Supporting
Information.
[20] It was found experimentally that adding HOP(O)(OPh)2 instead of formic
acid provides the products 4r and 4x in higher yields. However, the
reason for that is still not clear. The pka values are similar (pka(HCO2H)
= 3.77 in H2O and pka(HOP(O)(OPh)2) = 3.88 in DMSO), therefore we
assume the difference in yield is due to increased solubility.
Keywords: Carbonyl-olefin cross-metathesis • 1,3-Diol
formation • 1,3-Diol fragmentation • Hole-catalysis
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[22] For further information see Supporting Information.
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