Department of Inorganic Chemistry , Indian Association for the Cultivation of Science , 2A & 2B Raja S. C. Mullick Road , Jadavpur, Kolkata 700032 , India.
Inorg Chem. 2018 Aug 6;57(15):8769-8777. doi: 10.1021/acs.inorgchem.8b00421. Epub 2018 Jul 16.
α-Ketoglutarate-dependent nonheme halogenases catalyze the halogenation of aliphatic C-H bonds in the biosynthesis pathway of many natural products. An iron(IV)-oxo-halo species has been established as the active oxidant in the halogenation reactions. With an objective to emulate the function of the nonheme halogenases, two iron(II)-α-keto acid complexes, [(phdpa)Fe(BF)Cl] (1) and [(1,4-tpbd)Fe(BF)Cl] (2) (where phdpa = N,N-bis(2-pyridylmethyl)aniline, 1,4-tpbd = N,N, N',N'-tetrakis(2-pyridylmethyl)benzene-1,4-diamine, and BF = benzoylformate), have been prepared. The iron complexes are capable of carrying out the oxidative halogenation of aliphatic C-H bonds using O as the terminal oxidant. Although the complexes are not selective toward C-H bond halogenation, they are the only examples of nonheme iron(II)-α-keto acid complexes mimicking the activity of nonheme halogenases. The dinuclear complex (2) exhibits enhanced reactivity toward C-H bond halogenation/hydroxylation.
α-酮戊二酸依赖性非血红素卤化酶在许多天然产物的生物合成途径中催化脂肪族 C-H 键的卤化。已经确定铁(IV)-氧-卤化物物种是卤化反应中的活性氧化剂。为了模拟非血红素卤化酶的功能，我们制备了两种铁(II)-α-酮酸配合物，[(phdpa)Fe(BF)Cl]（1）和[(1,4-tpbd)Fe(BF)Cl]（2）（其中 phdpa = N,N-双(2-吡啶基甲基)苯胺，1,4-tpbd = N,N,N',N'-四(2-吡啶基甲基)苯-1,4-二胺，和 BF = 苯甲酰基甲酸酯）。这些铁配合物能够使用 O 作为末端氧化剂进行脂肪族 C-H 键的氧化卤化。尽管这些配合物对 C-H 键卤化没有选择性，但它们是非血红素铁(II)-α-酮酸配合物模拟非血红素卤化酶活性的唯一例子。双核配合物（2）对 C-H 键卤化/羟化反应表现出增强的反应性。
