Computational Investigations of Heme Carbenes and Heme Carbene Transfer Reactions
- 23 August 2019
- journal article
- review article
- Published by Wiley in Chemistry – A European Journal
- Vol. 25 (58), 13231-13247
- https://doi.org/10.1002/chem.201901984
Abstract
Engineered heme proteins and biomimetic iron porphyrins have been found to possess excellent catalytic properties for numerous carbene transfer reactions. Computational studies, including the use of DFT calculations and molecular dynamics simulations, have been employed to help understand some important mechanistic aspects of heme carbene transfer reactions. This review summarizes advances in the computational results published in the following two areas: 1) the electronic and geometric structures of heme carbenes; spectroscopic properties; and effects of carbene substituent, porphyrin substituent, axial ligand, and spin state on heme carbene formation; and 2) mechanisms of heme carbenoid X-H (X=C, Si, B, N, S) insertions and cyclopropanation, including effects of heme carbene structural components and protein environment, as well as oxidation state and spin state. A brief outlook of future development is also addressed.Keywords
This publication has 152 references indexed in Scilit:
- Olefin Cyclopropanation via Carbene Transfer Catalyzed by Engineered Cytochrome P450 EnzymesScience, 2013
- Organosilicon Molecules with Medicinal ApplicationsJournal of Medicinal Chemistry, 2012
- HNO Binding in a Heme Protein: Structures, Spectroscopic Properties, and StabilitiesJournal of the American Chemical Society, 2011
- Enzyme Reactivation by Hydrogen Peroxide in Heme-based Tryptophan DioxygenaseJournal of Biological Chemistry, 2011
- Unprecedented Fe(IV) Species in a Diheme Protein MauG: A Quantum Chemical Investigation on the Unusual Mössbauer Spectroscopic PropertiesThe Journal of Physical Chemistry Letters, 2010
- Mössbauer, NMR, Geometric, and Electronic Properties in S = 3/2 Iron PorphyrinsJournal of the American Chemical Society, 2009
- Catalytic C–H functionalization by metal carbenoid and nitrenoid insertionNature, 2008
- Selective, competitive and mechanism-based inhibitors of human cytochrome P450 2J2Archives of Biochemistry and Biophysics, 2007
- Estimation of Electronegativity Values of Elements in Different Valence StatesThe Journal of Physical Chemistry A, 2006
- Synthesis and Applications of β-Aminocarboxylic Acids Containing a Cyclopropane RingChemical Reviews, 2003