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  • Site-selective and versatile aromatic C-H functionalization by thianthrenation.

Site-selective and versatile aromatic C-H functionalization by thianthrenation.

Nature (2019-03-15)
Florian Berger, Matthew B Plutschack, Julian Riegger, Wanwan Yu, Samira Speicher, Matthew Ho, Nils Frank, Tobias Ritter
ABSTRACT

Direct C-H functionalization can quickly increase useful structural and functional molecular complexity1-3. Site selectivity can sometimes be achieved through appropriate directing groups or substitution patterns1-4-in the absence of such functionality, most aromatic C-H functionalization reactions provide more than one product isomer for most substrates1,4,5. Development of a C-H functionalization reaction that proceeds with high positional selectivity and installs a functional group that can serve as a synthetic linchpin for further functionalization would provide access to a large variety of well-defined arene derivatives. Here we report a highly selective aromatic C-H functionalization reaction that does not require a particular directing group or substitution pattern to achieve selectivity, and provides functionalized arenes that can participate in various transformations. We introduce a persistent sulfur-based radical to functionalize complex arenes with high selectivity and obtain thianthrenium salts that are ready to engage in different transformations, via both transition-metal and photoredox catalysis. This transformation differs fundamentally from all previous aromatic C-H functionalization reactions in that it provides direct access to a large number of derivatives of complex small molecules, quickly generating functional diversity with selectivity that is not achievable by other methods.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Thianthrene S-oxide, ≥95%
Sigma-Aldrich
2,3,7,8-Tetrafluorothianthrene-S-oxide, ≥95%