Herein, we report an enantioselective hydroamination of alkenes with sulfonamides, enabled by proton-coupled electron transfer (PCET). The PCET step proceeds through the simultaneous oxidation and deprotonation of a sulfonamide N–H bond by an iridium photocatalyst and chiral phosphate base, respectively. We propose that residual hydrogen bonding interactions between the resulting neutral sulfonamidyl radical and neutral conjugate chiral phosphoric acid induce asymmetry during the subsequent C–N bond formation. This reaction has been demonstrated for a variety of sulfonamides in an intramolecular cyclization reaction with selectivities up to 95% ee. These results demonstrate that neutral, open-shell hydrogen bonding interactions can be applied as a design principle for asymmetric reactions with radical intermediates.

Enantioselective hydroamination of alkenes with sulfonamides enabled by proton-coupled electron transfer

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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