TY - JOUR
T1 - The effect of heme environment on the hydrogen abstraction reaction of camphor in P450cam catalysis
T2 - A QM/MM study
AU - Altun, Ahmet
AU - Guallar, Victor
AU - Friesner, Richard A.
AU - Shaik, Sason
AU - Thiel, Walter
PY - 2006/3/29
Y1 - 2006/3/29
N2 - The discrepancies between the published QM/MM studies (Schöneboom, J. C.; Cohen, S.; Lin, H.; Shaik, S.; Thiel, W. J. Am. Chem. Soc. 2004, 126, 4017; Guallar, V.; Friesner, R. A. J. Am. Chem. Soc. 2004, 126, 8501) on H-abstraction of camphor in P450cam have largely been resolved. The crystallographic water molecule 903 situated near the oxo atom of Compound I acts as a catalyst for H-abstraction, lowering the barrier by about 4 kcal/mol. Spin density at the A-propionate side chain of heme can occur in the case of incomplete screening but has no major effect on the computed barrier.
AB - The discrepancies between the published QM/MM studies (Schöneboom, J. C.; Cohen, S.; Lin, H.; Shaik, S.; Thiel, W. J. Am. Chem. Soc. 2004, 126, 4017; Guallar, V.; Friesner, R. A. J. Am. Chem. Soc. 2004, 126, 8501) on H-abstraction of camphor in P450cam have largely been resolved. The crystallographic water molecule 903 situated near the oxo atom of Compound I acts as a catalyst for H-abstraction, lowering the barrier by about 4 kcal/mol. Spin density at the A-propionate side chain of heme can occur in the case of incomplete screening but has no major effect on the computed barrier.
UR - http://www.scopus.com/inward/record.url?scp=33645452758&partnerID=8YFLogxK
U2 - 10.1021/ja058196w
DO - 10.1021/ja058196w
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C2 - 16551096
AN - SCOPUS:33645452758
SN - 0002-7863
VL - 128
SP - 3924
EP - 3925
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 12
ER -