TY - JOUR
T1 - Two-state reactivity mechanisms of hydroxylation and epoxidation by cytochrome P-450 revealed by theory
AU - Shaik, Sason
AU - De Visser, Samuël P.
AU - Ogliaro, François
AU - Schwarz, Helmut
AU - Schröder, Detlef
PY - 2002/10/1
Y1 - 2002/10/1
N2 - Recent computational studies of alkane hydroxylation and alkene epoxidation by a model active species of the enzyme cytochrome P-450 reveal a two-state reactivity (TSR) scenario in which the information content of the product distribution is determined jointly by two states. TSR is used to reconcile the dilemma of the consensus 'rebound mechanism' of alkane hydroxylation, which emerged from experimental studies of ultra-fast radical clocks. The dilemma, stated succinctly as 'radicals are both present and absent and the rebound mechanism is both right and wrong', is simply understood once one is cognizant that the mechanism operates by two states, one low-spin (LS) the other high-spin (HS). In both states, bond activation proceeds in a manner akin to the rebound mechanism, but the LS mechanism is effectively concerted, whereas the HS is stepwise with incursion of radical intermediates.
AB - Recent computational studies of alkane hydroxylation and alkene epoxidation by a model active species of the enzyme cytochrome P-450 reveal a two-state reactivity (TSR) scenario in which the information content of the product distribution is determined jointly by two states. TSR is used to reconcile the dilemma of the consensus 'rebound mechanism' of alkane hydroxylation, which emerged from experimental studies of ultra-fast radical clocks. The dilemma, stated succinctly as 'radicals are both present and absent and the rebound mechanism is both right and wrong', is simply understood once one is cognizant that the mechanism operates by two states, one low-spin (LS) the other high-spin (HS). In both states, bond activation proceeds in a manner akin to the rebound mechanism, but the LS mechanism is effectively concerted, whereas the HS is stepwise with incursion of radical intermediates.
UR - http://www.scopus.com/inward/record.url?scp=0036802621&partnerID=8YFLogxK
U2 - 10.1016/S1367-5931(02)00363-0
DO - 10.1016/S1367-5931(02)00363-0
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C2 - 12413538
AN - SCOPUS:0036802621
SN - 1367-5931
VL - 6
SP - 556
EP - 567
JO - Current Opinion in Chemical Biology
JF - Current Opinion in Chemical Biology
IS - 5
ER -