10.1002/anie.201910830
Angewandte Chemie International Edition
COMMUNICATION
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In conclusion, we report herein a novel method to synthesize
ethers with vicinal SF5 substituent by a one-step protocol
including photoredox catalysis. The products described herein
bear a new structural motif with two functional groups, the SF5
and the alkoxy substituents, and thereby represent important new
SF5-building blocks. Moreover, the alkoxy substituents allow
further transformation by elimination and azidation. Our results
complement the closed-shell deoxyfluorination type photoredox
chemistry of SF6 and pave the way to use SF6 as a highly valuable
SF5-transfer reagent if properly activated by highly reducing
photoredox catalysts. Our method does not only tolerate protic
groups and high concentrations of alcohols, but uses them as
nucleophiles. Unfortunately, the presence of water as nucleophile
is strictly prohibited by irreversible sulfoxidation of the photoredox
catalyst. Despite this resctriction, the corresponding SF5-alcohol
can be pepared by the use of sterically demanding alcohols. Toxic
reagents are completely avoided, and instead, non-toxic SF6 is
applied as chemical reagent. Our vision is to reuse SF6 after
technical applications for chemical synthesis of valuable SF5-
molecules, instead of simply destroying it. Thereby, the proposed
benign potential of the SF5 substituent in medicinal, agro- and
material chemistry may be exploited in the future. In combination
with light as energy source, the basis for a high level of
sustainability is set.
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Experimental Section
All experimental details are described in the Supporting Information.
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Acknowledgements
Financial support by the Deutsche Forschungsgemeinschaft
(grant Wa 1386/16-2) and KIT is gratefully acknowledged. D.R.
thanks the Landesgraduiertenstiftung Baden-Württemberg for a
doctoral fellowship and the GRK 1626 for their qualification
program. Further we thank Prof. Dr. Frank Breher and Prof. Dr.
Michael A. R. Meier as well as Prof. Dr. M. Wilhelm for sharing
parts of their infrastructure. We kindly thank M. Sc. Bernhard
Birenheide for solving the XRD structure of 9.
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Conflicts of interest
D. R. and H.A.W. filed a patent application of the reported method.
Keywords: photochemistry • addition • photocatalysis • electron
transfer • phenothiazine.
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