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Reactions of arynes with TEMPO involving 1,5‐ or 1,4‐HAT to give bisalkoxyamines 6 a–d. Reaction conditions: 5 (0.20 mmol, 1.0 equiv), TEMPO (1.0 mmol, 5.0 equiv), CsF (0.60 mmol, 3.0 equiv), 18‐crown‐6 ether (0.60 mmol, 3.0 equiv), and n‐hexane (2.0 mL). [a] Reaction condition: 5 e (1.0 mmol, 1.0 equiv), TEMPO (3.0 mmol, 3.0 equiv), CsF (3.0 mmol, 3.0 equiv), and MeCN (10 mL). Yields represent isolated yields.
