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The enantioselective construction of axially chiral aryl‐naphthopyran skeletons was realized by organocatalytic atroposelective intramolecular [4+2] cycloaddition of in situ generated vinylidene ortho‐quinone methides, from 2‐ethynylphenol derivatives, with alkynes. Through this method, the heteroatropisomers were obtained with excellent yields and enantioselectivities. Moreover, a speculative model...
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