Enantioselective intramolecular C-H amination catalyzed by engineered cytochrome P450 enzymes in vitro and in vivo.

Nitrogen activation: Though P450 enzymes are masters of oxygen activation and insertion into C-H bonds, their ability to use nitrogen for the same purpose has so far not been explored. Engineered variants of cytochrome P450_(BM3) have now been found to catalyze intramolecular C-H aminations in azide substrates. Mutations to two highly conserved residues significantly increased this activity.

[1]  S. Gellman,et al.  Tosylamidation of cyclohexane by a cytochrome P-450 model , 1982 .

[2]  Michael T. Green.  C-H bond activation in heme proteins: the role of thiolate ligation in cytochrome P450. , 2009, Current opinion in chemical biology.

[3]  Frank Hollmann,et al.  Synthetic cascades are enabled by combining biocatalysts with artificial metalloenzymes , 2012, Nature Chemistry.

[4]  X. Zhang,et al.  Catalytic C-H functionalization by metalloporphyrins: recent developments and future directions. , 2011, Chemical Society reviews.

[5]  J. D. Bois,et al.  Metal-catalyzed oxidations of C-H to C-N bonds. , 2010, Topics in current chemistry.

[6]  D. Mansuy,et al.  Allylic amination of alkenes by tosyliminoiodobenzene: manganese porphyrins as suitable catalysts , 1988 .

[7]  G. Huisman,et al.  Engineering the third wave of biocatalysis , 2012, Nature.

[8]  A. Glieder,et al.  Monooxygenases as biocatalysts: Classification, mechanistic aspects and biotechnological applications. , 2010, Journal of biotechnology.

[9]  N. Turner.  Ammonia lyases and aminomutases as biocatalysts for the synthesis of α-amino and β-amino acids. , 2011, Current opinion in chemical biology.

[10]  M. J. Coon,et al.  Multiple mechanisms and multiple oxidants in P450-catalyzed hydroxylations. , 2003, Archives of biochemistry and biophysics.

[11]  R. White,et al.  Aliphatic hydroxylation by cytochrome P-450: evidence for rapid hydrolysis of an intermediate iron-nitrene complex , 1984 .

[12]  Sason Shaik,et al.  Mechanism of oxidation reactions catalyzed by cytochrome p450 enzymes. , 2004, Chemical reviews.

[13]  P. Cullis,et al.  Control of the stereo-selectivity of styrene epoxidation by cytochrome P450 BM3 using structure-based mutagenesis. , 2011, Metallomics : integrated biometal science.

[14]  Frances H. Arnold,et al.  Olefin Cyclopropanation via Carbene Transfer Catalyzed by Engineered Cytochrome P450 Enzymes , 2013, Science.

[15]  D. Sherman,et al.  Diversity of P450 enzymes in the biosynthesis of natural products. , 2012, Natural product reports.

[16]  E. Gallo,et al.  Chiral porphyrin complexes of cobalt(II) and ruthenium(II) in catalytic cyclopropanation and amination reactions , 2006 .

[17]  P. Dauban,et al.  Iminoiodanes and C-NBond Formation in Organic Synthesis , 2003 .

[18]  J. Dawson,et al.  Probing structure-function relations in heme-containing oxygenases and peroxidases. , 1988, Science.

[19]  J. Groves,et al.  Hydroxylation and epoxidation catalyzed by iron-porphine complexes. Oxygen transfer from iodosylbenzene , 1979 .

[20]  Thomas R. Ward,et al.  Biotinylated Rh(III) Complexes in Engineered Streptavidin for Accelerated Asymmetric C–H Activation , 2012, Science.

[21]  R. Friesner,et al.  Quantum chemical studies of methane monooxygenase: comparision with P450. , 2002, Current opinion in chemical biology.

[22]  X. Zhang,et al.  Cobalt-catalyzed intramolecular C-H amination with arylsulfonyl azides. , 2007, Organic letters.

[23]  D. Janssen,et al.  Priming ammonia lyases and aminomutases for industrial and therapeutic applications. , 2013, Current opinion in chemical biology.

[24]  S. Bell,et al.  P450(BM3) (CYP102A1): connecting the dots. , 2012, Chemical Society reviews.

[25]  S. Gellman,et al.  Functionalized nitrogen atom transfer catalyzed by cytochrome P-450 , 1985 .

[26]  T. Uchida,et al.  Enantioselective intramolecular benzylic C-H bond amination: efficient synthesis of optically active benzosultams. , 2011, Angewandte Chemie.