Selective C–H halogenation over hydroxylation by non-heme iron(iv)-oxo

Abstract

Synthetic non-heme iron-oxo and iron-halide complexes promote selective halogenation of the sp3-C–H bonds via hydrogen atom abstraction and halide rebound phenomenon.

Interplay Between Steric and Electronic Effects: A Joint Spectroscopy and Computational Study of Nonheme Iron(IV)‐Oxo Complexes

“…In particular, the sixth coordination position, trans to the N ax , is occupied by the solvent CH 3 CN in both complexes, but there is a substantial bending in the N ax ‐Fe‐solvent axis for 3 a (167.5°), as compared to 2 a (179.3°). This is the largest bend observed among the fellow structures (Table ) and is close to that in 4 a reported by Rana et al., in which a triflate counter‐anion occupies the apical position instead of a solvent molecule . The huge tilt accounts for an induced steric effect imparted by the methyl groups in the structure of 3 a .…”

Chemoselectivity in the Oxidation of Cycloalkenes with a Non-Heme Iron(IV)-Oxo-Chloride Complex: Epoxidation vs. Hydroxylation Selectivity

“…In solution, many effects can play a role. For example, formation of relatively stable intermediates after the hydrogen transfer opens a possibility for a cage escape mechanism [88,89].…”

The Protein’s Role in Substrate Positioning and Reactivity for Biosynthetic Enzyme Complexes: The Case of SyrB2/SyrB1

“…7 As a result, the development of mimetic inorganic complexes of these enzymes has been an area of intense focus. [8][9][10][11][12] Non-heme iron enzymes differ from their mimetics by operating under a distinct catalytic paradigm in which the enzyme environment protects a deeply buried but reactive metal center and controls specificity in part through substrate delivery. [1][2][3][4][5][6] One such enzyme is SyrB2 [13][14] , an Fe/α-ketoglutarate (αKG)-dependent halogenase [13][14][15][16][17][18][19][20] from Pseudomonas syringae in which the Fe(II) center is coordinated by two protein His, one Cl, and αKG.…”

“…cluster min avg +/-std max min avg +/-std max min avg +/-std max min avg +/-std max 0 3.10 3.41 +/-0 12. 3.84 3.03 3.43 +/-0.11 3.79 3.23 3.59 +/-0.11 4.00 3.83 4.23 +/-0.1 4.55 1 3.11 3.41 +/-0.11 3.81 2.96 3.42 +/-0.11 3.75 3.19 3.58 +/-0.11 3.98 3.87 4.22 +/-0.10 4.59 2 3.06 3.41 +/-0.12 3.80 2.99 3.42 +/-0.11 3.74 3.27 3.59 +/-0.11 4.00 3.81 4.22 +/-0.10 4.57 3 3.09 3.41 +/-0.12 3.82 3.04 3.41 +/-0.12 3.75 3.26 3.58 +/-0.11 3.98 3.82 4.22 +/-0.10 4.53 4 3.12 3.41 +/-0.12 3.78 2.94 3.41 +/-0.12 3.70 3.27 3.58 +/-0.11 3.93 3.85 4.22 +/-0.10 4cluster min avg +/-std max min avg +/-std max min avg +/-std max min avg +/-std max 0 3.04 3.36 +/-0.12 3.95 3.75 4.18 +/-0.11 4.66 4.49 4.87 +/-0.12 5.46 4.89 5.34 +/-0.13 5.82 1 3.06 3.41 +/-0.11 3.93 3.72 4.07 +/-0.10 4.40 4.38 3.76 +/-0.14 4.39 4.26 4.68 +/-0.12 5.07 2 3.15 3.34 +/-0.11 3.64 3.95 4.20 +/-0.12 4.51 4.65 4.85 +/-0.11 5.13 4.87 5.21 +/-0.16 5.58 3 3.16 3.32 +/-0.09 3.51 3.98 4.19 +/-0.11 4.34 4.69 4.84 +/-0.09 5.04 4.95 5.21 +/-0.13 5.48 4 3.21 3.32 +/-0.10 3.51 4.08 4.23 +/-0.10 4.39 4.65 4.82 +/-0.12 5.08 5.10 5.21 +/-0.05 5.28 ax-NO Thr methyl C-Cl methyl C-N ethyl C-Cl ethyl C-N cluster min avg +/-std max min avg +/-std max min avg +/-std max min avg +/-std max 0 3.06 3.39 +/-0.11 3.79 4.04 4.50 +/-0.11 5.02 3.27 3.58 +/-0.11 4.00 4.42 4.90 +/-0.14 5.48 1 3.08 3.38 +/-0.11 3.75 4.11 4.49 +/-0.11 4.97 3.20 3.59 +/-0.14 4.39 4.37 4.87 +/-0.13 5.35 2 3.10 3.38 +/-0.11 3.82 4.16 4.49 +/-0.11 4.89 3.27 3.58 +/-0.11 4.02 4.40 4.89 +/-0.14 5.30 3 3.06 3.38 +/-0.11 3.72 4.08 4.48 +/-0.12 4.90 3.27 3.62 +/-0.18 4.86 4.43 4.89 +/-0.14 5.37 4 3.17 3.24 +/-0.07 3.31 4.49 4.65 +/-0.16 4.81 3.48 3.51 +/-0.03 3.53 5.00 5.07 +/-0.07 5cluster min avg +/-std max min avg +/-std max min avg +/-std max min avg +/-std max 0 3.21 3.59 +/-0.11 4.08 2.90 3.19 +/-0.09 3.62 3.18 3.51 +/-0.11 4.06 4.13 4.47 +/-0.09 4.84 1 3.25 3.59 +/-0.11 4.08 2.89 3.19 +/-0.09 3.65 3.19 3.51 +/-0.11 4.05 4.18 4.47 +/-0.09 4.84 2 3.19 3.59 +/-0.11 4.02 2.89 3.19 +/-0.09 3.57 3.16 3.51 +/-0.11 3.91 4.15 4.47 +/-0.09 4.84 3 3.36 3.50 +/-0.14 3.68 3.16 3.22 +/-0.05 3.31 3.39 3.50 +/-0.09 3.63 4.43 4.50 +/-0.05 4.58 4 3.49 3.55 +/-0.06 3.61 3.23 3.29 +/-0.05 3.34 3.41 3.47 +/-0.06 3.52 4.47 4.55 +/-0.09 4.64 eq-NO Aba methyl C-Cl methyl C-N ethyl C-Cl ethyl C-N cluster min avg +/-std max min avg +/-std max min avg +/-std max min avg +/-std max 0 3.02 3.28 +/-0.09 3.64 3.79 4.16 +/-0.17 5.10 3.27 3.76 +/-0.14 4.31 4.85 5.38 +/-0.17 6cluster min avg +/-std max min avg +/-std max min avg +/-std max min avg +/-std max 0 3.14 3.56 +/-0.14 4.17 4.01 4.62 +/-0.24 5.42 3.27 3.62 +/-0.12 4.17 4.37 5.07 +/-0.19 5.70 1 3.13 3.56 +/-0.14 4.10 4.04 4.61 +/-0.24 5.41 3.30 3.62 +/-0.11 4.17 4.36 5.07 +/-0.19 5.67 2 3.20 3.56 +/-0.13 3.97 4.09 4.43 +/-0.12 4.74 3.30 3.61 +/-0.12 3.99 4.50 4.94 +/-0.15 5.27 3 3.25 3.48 +/-0.11 3.83 3.88 4.18 +/-0.10 4.41 3.23 3.49 +/-0.10 3.68 4.96 5.23 +/-0.11 5.54 4 3.75 3.75 +/-0.00 3.75 5.16 5.16 +/-0.00 5.16 3.79 3.79 +/-0.00 3.79 5.21 5.21 +/-0.00 5.21…”