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An unprecedented (5 + 2)-cycloaddition reaction of ortho-hydroxyethyl phenol and internal alkyne was developed. This Rh(III)-catalyzed reaction provided benzoxepine derivatives which have very high biological significance. A wide range of ortho-hydroxyethyl phenols and internal alkynes were studied to provide the benzoxepines in high yields.

Graphical abstract: Rh(iii)-catalyzed (5 + 2)-cycloaddition reactions of ortho-hydroxyethyl phenols with internal alkynes: efficient synthesis of benzoxepines

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