TY - JOUR
T1 - Computational Investigations of Heme Carbenes and Heme Carbene Transfer Reactions
AU - Zhang, Yong
N1 - Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/10/17
Y1 - 2019/10/17
N2 - 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.
AB - 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.
KW - biocatalysis
KW - carbenoids
KW - computational chemistry
KW - heme proteins
KW - reaction mechanisms
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U2 - 10.1002/chem.201901984
DO - 10.1002/chem.201901984
M3 - Review article
C2 - 31306529
AN - SCOPUS:85071016712
SN - 0947-6539
VL - 25
SP - 13231
EP - 13247
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 58
ER -