This work reports the design and synthesis of a series of 5membered and 6-membered N-hydroxyimides flanked by lipophilic alkyl groups adjacent to carbonyl groups, aiming to endow lipophilicity and tolerance toward ring opening degradation. Their solubility in cyclohexane was 5-20 times higher than those of unsubstituted N-hydroxyphthalimide (NHPI) and even 3-10 times higher than a formerly known lipophilic NHPI analog bearing a long alkyl ester. UV-Vis spectroscopy determined the rate constants of first-order decay of N-oxyls, which revealed enhanced stability of 3,5-di-tert-butyl-NHPI and Nhydroxyglutarimide flanked by spiro-cyclohexanes compared with that of NHPI. Their bond dissociation energies were assessed by EPR spectroscopy and DFT calculation, suggesting these lipophilic N-hydroxyimides catalyzed aerobic cyclohexane oxidation under neat conditions with up to 60 turnovers, which is the highest among hitherto reported reactions under neat conditions.
The cover feature image shows aerobic C‐H oxidation of hydrocarbon by lipophilic N‐hydroxyimides. Novel N‐hydroxyimides flanked by alkyl substituents exhibited excellent solubility in hydrocarbons, allowing high‐turnover oxidation of neat cyclohexane under O2 atmosphere. Cover designed by Tomomi Kato. More information can be found in the Research Article by R. Nakano, M. Yamashita, and co‐workers.
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