[3,3]‐Sigmatropic Rearrangements of Naphthyl 1‐Propargyl Ethers: para‐Propargylation and Catalytic Asymmetric Dearomatization

The para-Claisen rearrangement of aryl 1-propargyl ethers involves two-step [3,3]-sigmatropic rearrangements and dearomatization process, which has high activation barriers and is of challenge. Here we discovered thermal para-Claisen rearrangement of naphthyl 1-propargyl ethers, and it enabled the formation of formal para-C-H propargylation products upon rearomatization. Chirality transfer occurred if optically active propargyl ethers were employed, leading to the construction of aryl/propargyl-containing stereogenic centers. Moreover, catalytic asymmetric dearomatization of naphthyl 1-propargyl ethers with different substitution at para-position gave access to benzocyclohexenones bearing all-carbon quaternary stereocenters. The reaction was accelerated by a chiral N,N'-dioxide/Co(OTf)2 complex catalyst to achieve high yields (up to 98 %) and high enantioselectivities (up to 93 % ee). The DFT calculations and experimental results provided important clues to clarify the para-Claisen rearrangement process as well as the chiral induction and remote delivery.