Methane Monooxygenase Mimic Asymmetric Oxidation: Self-Assembling μ-Hydroxo, Carboxylate-Bridged Diiron(III)-Catalyzed Enantioselective Dehydrogenation.

Abstract

Mimicking naturally occurring metalloenzymes to enrich the diversity of catalytic asymmetric oxidation reactions is a long-standing goal for modern chemistry. Toward this end, a range of methane monooxygenase (MMO) mimic chiral carboxylate-bridged (μ-hydroxo) 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.