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A Co(III)-catalyzed dual C–C coupling of sterically hindered tertiary allylic alcohols (TAA) with aldehydes via carbon-skeleton rearrangement has been developed. This transformation features a cascade 1,3-aryl transposition and highly regioselective cross-coupling at the C2- and C3- positions of TAA. The combination of experimental and computational studies revealed the synergetic mechanism of Co(III)-catalysts and B(C6F5)3 to enable β-aryl elimination and direct selective trapping of reactive intermediates.
Yang et al. (Tue,) studied this question.