An alkoxyl radical guided strategy for site-selective functionalization of unactivated methylene and methine C-H bonds enabled by an Fe -catalyzed redox process is described. The mild, expeditious, and modular protocol allows efficient remote aliphatic fluorination, chlorination, amination, and alkynylation of structurally and electronically varied primary, secondary, and tertiary hydroperoxides with excellent functional-group tolerance. The application for one-pot 1,4-hydroxyl functionalization of non-oxygenated alkane substrates initiated by aerobic C-H oxygenation is also demonstrated.

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A nonenzymatic iron-catalyzed dehydrogenative kinetic resolution of cyclic secondary amines using air as an oxidant has been reported. The economical and practical method is applicable to a series of cyclic benzylic amines, including 5,6-dihydrophenanthridines and 1,2-dihydroquinolines, with diverse functional groups at the α position in high yields with excellent enantioselectivities. The direct dehydrogenative kinetic resolution of advanced intermediates of bioactive molecules that are difficult to access using existing catalytic asymmetric synthetic strategy was also demonstrated.

Mimicking naturally occurring metalloenzymes to enrich the diversity of catalytic asymmetric oxidation reactions is a longstanding goal for modern chemistry. Toward this end, a range of methane monooxygenase (MMO) mimic chiral carboxylate-bridged (μhydroxo) diiron(III) dimer complexes using salan as basal ligand and sodium aryl carboxylate as additive have been designed and synthesized. The chiral diiron complexes exhibit efficient catalytic reactivity in dehydrogenative kinetic resolution of indolines using environmentally benign hydrogen peroxide as oxidant. In particular, complex C9 bearing sterically encumbered salan ligands and a 2-naphthoate bridge is identified as the optimal catalyst in terms of chiral recognition. Further investigation reveals that this MMO mimic chiral catalyst can be readily generated by self-assembly under the dehydrogenation conditions. The self-assembling catalytic system is applicable to a series of indolines with multiple stereocenters and diverse substituent patterns in high efficiency with a high level of chiral recognition (selectivity factor up to 153). Late-stage dehydrogenative kinetic resolution of bioactive molecules is further examined.

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