Rh(III)-Catalyzed Stereoselective C–C Bond Cleavage of ACPs with N -Phenoxyacetamides: The Critical Role of the Nucleophilic Directing Group

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Rh(III)-catalyzed redox-neutral chemodivergent coupling of N -phenoxyacetamides and alkylidenecyclopropanes (ACPs) has been documented. The reaction proceeds via C–H activation, regioselective migratory insertion and stereoselective β-carbon elimination followed by β-hydride elimination, resulting in o -dienylation of phenols in nonpolar solvents, whereas [3 + 2]-annulation leading to dihydrobenzofurans was realized in polar fluorinated solvents. It was observed that the nucleophilic directing group controls the elimination of β-carbon and so plays a vital role for achieving high stereoselectivities. The synthetic utility of the dienylation and annulation was demonstrated by carrying out gram scale reactions and further derivatization.