Parallel and competitive pathways for substrate desaturation, hydroxylation, and radical rearrangement by the non-heme diiron hydroxylase AlkB

…, M Pender-Cudlip, RN Austin, J Shanklin…

Index: Cooper, Harriet L. R.; Mishra, Girish; Huang, Xiongyi; Pender-Cudlip, Marilla; Austin, Rachel N.; Shanklin, John; Groves, John T. Journal of the American Chemical Society, 2012 , vol. 134, # 50 p. 20365 - 20375

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Citation Number: 17

Abstract

A purified and highly active form of the non-heme diiron hydroxylase AlkB was investigated using the diagnostic probe substrate norcarane. The reaction afforded C2 (26%) and C3 (43%) hydroxylation and desaturation products (31%). Initial C–H cleavage at C2 led to 7% C2 hydroxylation and 19% 3-hydroxymethylcyclohexene, a rearrangement product characteristic of a radical rearrangement pathway. A deuterated substrate analogue, 3, 3, ...