from first principles PP-I-1

OY-II-3Highly Efficient, Regioselective and Stereospecific Oxidationof Non-Activated Aliphatic C-H Groups with H 2 O 2 ,Catalyzed by Aminopyridine Manganese ComplexesOttenbacher R.V. 1,2 , Talsi E.P. 1 , Bryliakov K.P. 11 Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia2 Novosibirsk State University, Novosibirsk, Russiar_o_m_a_h_a@mail.ruThe selective functionalization of non-activated C-H groups remains one of the greatestchallenges in synthetic chemistry since such reactions would disclose new and morestraightforward synthetic routes towards complex organic molecules. The oxidations of C-Hgroups catalyzed by enzymes are widely present in nature. In contrast, very few examples ofselective and environmentally benign C-H oxidations catalyzed by synthetic non-heme ironcomplexes are known [1, 2], albeit with low-to-moderate efficiencies (10 up to 100). Here wereport the C-H oxidation reactivity of Mn complexes 1-3 (Scheme 1): they have demonstratedpreviously unachievable high site-selectivities and high efficiencies at the same time.Scheme 1. Manganese(II) complexes consideredScheme 2. Catalytic oxidation of cyclohexaneMn complexes 1-3 were employed as catalysts for oxidation of a number of aliphaticsubstrates with H 2 O 2 in the presence of acetic acid. Cyclohexane was oxidized (Scheme 2)with up to 5.1 A/K ratio under model conditions ([H 2 O 2 ]