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The photolysis reactions of (8‐cyano‐7‐hydroxyquinolin‐2‐yl)methyl (CyHQ)‐caged amines have been investigated using time‐resolved spectroscopy methods. Unexpectedly, an unconventional Hofmann‐Martius rearrangement reaction with high yield and regioselectivity occurred during the photolysis of some CyHQ‐protected dialkylanilines (such as compounds 1a and 2a). To have more insights into the mechanism...
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