Non-heme-iron (NH-Fe) enzymes activate O2 for an impressive array of biomedically, agriculturally, and environmentally important oxidation reactions. Our past decade's work has established the intermediacy of iron(IV)-oxo (FeIV=O or ferryl) complexes in the reactions of several NH-Fe enzymes.1 In five of these enzymes, the ferryl complexes generate substrate radicals by abstracting hydrogen (H�) from unactivated aliphatic carbons,2-6 leading to formation of new C�O,2-4 C�Cl/Br,5,6 and C�S bonds.1 Energized by our past success in rationalizing the divergent outcomes of the a-ketoglutarate(aKG)-dependent aliphatic hydroxylases and halogenases,7 we now seek to understand several additional transformations, including 1,3-dehydrogenation of alcohol to epoxide, stereo-inversion of a chiral carbon, and desaturation and cleavage of C�C bonds, which are mediated by other NH-Fe enzymes and for which our unpublished data implicate ferryl complexes as the initiating intermediates. Progress toward an understanding of this manifold of chemically challenging transformations will be presented.1. Krebs, C., Galonic, D.; Walsh, C.T.; Bollinger, J.M., Jr. Acc. Chem. Res., 2007 , 40, 484-492.2. Price, J. C.; Barr, E.W.; Tirupati, B.; Bollinger, J.M., Jr.; Krebs, C.; Biochemistry, 2003 , 42, 7497-7508.3. Price, J.C.; Barr, E.W.; Glass, T.E.; Krebs, C.; Bollinger, J.M., Jr.; J. Am. Chem. Soc., 2003 , 125, 13008-13009.4. Hoffart, L. M.; Barr, E.W.; Guyer, R.B.; Bollinger, J.M., Jr.; Krebs, C. Proc. Natl. Acad. Sci. USA, 2006 , 103, 14738-14743.5. Galonic, D.P.; Barr, E.W.; Walsh, C.T.; Bollinger, J.M., Jr.; Krebs, C. Nat. Chem. Biol., 2007 , 3, 113-116.6. Matthews, M.L.; Krest, C.M.; Barr, E.W.; Vaillancourt, F.H.; Walsh, C.T.; Green, M.T.; Krebs, C.; Bollinger, J.M., Jr. Biochemistry, 2009 , 48, 4331-4343.7. Matthews, M.L.; Neumann, C.S.; Miles, L.A.; Grove, T.L.; Booker, S.J.; Krebs, C; Walsh, C.T.; Bollinger, J.M., Jr, Proc. Natl. Acad. Sci. USA,2009 , 106, 17723-17728.

Frontiers beyond the hydroxylation paradigm in the diverse chemistry of nonhemeFe(IV)-oxo (Ferryl) enzyme intermediates

245th National Meeting (2013)

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