Amine-Catalyzed Copper-Mediated C-H Sulfonylation of Benzaldehydes via a Transient Imine Directing Group

Transient directing groups (TDGs) can provide a powerful means for C-H functionalization without requiring additional steps for directing group introduction and removal. We report the first use of a TDG in combination with copper to effect C-H functionalization. The regioselective copper mediated beta-C(sp(2))-H sulfonylation of aldehydes with sulfinate salts is accomplished using catalytic beta-alanine to form a transient imine A broad range of sulfonylated benzaldehydes are prepared using copper fluoride as both copper source and oxidant, involving a [5,6] cupracyclic intermediate. gamma-(peri)-Sulfonylation of napthyl and phenanthrenyl carboxaldehydes is achieved through [6,6] cupracyclic intermediates. Further derivatisation of the aldehyde products is demonstrated. Kinetic experiments and Hammett analysis suggest the turnover limiting step to be a concerted asynchronous C-H cleavage via a dearomative Wheland-type transition state.