In biology, the repair of cytotoxic N-methylated nucleic acids by  the a-ketoglutarate-dependent dioxygenase, AlkB, occurs by  hydroxylation of the N-methyl C-H bond followed by release of  formaldehyde and the demethylated nucleic acid.  Similarly, cytochrome  P450 metabolizes the breakdown of N,N-dimethylformamide (DMF) by  first hydroxylating one of the N-methyl C-H bonds, yielding N-hydroxy-N-methylformamide  (HMMF), which then decomposes to release N-methylformamide and  formaldehyde.  Despite these examples of N-methyl C-H bond  hydroxylation in biology, in synthetic chemistry, hydroxylation of the N-methyl  C-H bonds of DMF is rare.  Herein we report an iron(II) complex (Ph4P[Fe(N(o-PhNC(O)Ph)3)(NCCH3)],  [Fe(LPh)(NCCH3)]-) that, in the  presence of excess oxygen atom transfer reagent, iodosobenzene,  catalyzes the hydroxylation of an N-methyl C-H bond of DMF to  form HMMF.  A product-inhibited byproduct of the reaction, Ph4P[FeIII(LPh)(OMMF)]  (where OMMF = (N-methylformamido)methanolate), has been  structurally, spectroscopically, and spectrometrically characterized.  The synthesis of this species by in situ oxidation of Ph4P[FeII(LPh)(OMMF)]  will also be discussed.

Catalytic hydroxylation of N,N-dimethylformamide by an Fe(II) complex

243rd National Meeting (2012)

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