Literature summary for 1.11.1.10 extracted from

Chatfield, D.C.; Morozov, A.N.
Proximal pocket controls alkene oxidation selectivity of cytochrome P450 and chloroperoxidase toward small, nonpolar substrates (2018), J. Phys. Chem. B, 122, 7828-7838 .

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Natural Substrates/ Products (Substrates)

Natural Substrates	Organism	Comment (Nat. Sub.)	Natural Products	Comment (Nat. Pro.)	Rev.	Reac.
RH + chloride + H2O2	Leptoxyphium fumago	-	RCl + 2 H2O	-	?

Organism

Organism	UniProt	Comment	Textmining
Leptoxyphium fumago	P04963	Caldariomyces fumago	-

Reaction

Reaction	Comment	Organism	Reaction ID
RH + chloride + H2O2 = RCl + 2 H2O	substrate specificity and reaction mechanism, overview. Relative favorability of catalytic epoxidation and allylic hydroxylation of olefins, a type of alkene oxidation selectivity. The selectivity for epoxidation versus can be rationalized in terms of the proximal pocket's modulation of the thiolate's electron push and consequent influence on the heme redox potential and the basicity of the trans ligand	Leptoxyphium fumago	a

Substrates and Products (Substrate)

Substrates	Comment Substrates	Organism	Products	Comment (Products)	Rev.	Reac.
additional information	theoretical analysis of the influence of the proximal pockets of cytochrome P450CAM and chloroperoxidase (CPO) on the relative favorability of catalytic epoxidation and allylic hydroxylation of olefins, a type of alkene oxidation selectivity. Quantum mechanical models of the active site are employed to isolate the proximal pocket's influence on the barrier for the selectivity-determining step for each reaction, using cyclohexene and cis-beta-methylstyrene as substrates. The proximal pocket shows preference for epoxidation, the largest value being for CPO, converting the active heme-thiolate moiety from being intrinsically hydroxylation-selective to being intrinsically epoxidation-selective. The proximal pocket is the key determinant of alkene oxidation selectivity. The selectivity for epoxidation can be rationalized in terms of the proximal pocket's modulation of the thiolate's electron push and consequent influence on the heme redox potential and the basicity of the trans ligand. The ratio of epoxidation to allylic hydroxylation products [C=C/C-H ratio or alkene oxidation selectivity (AOS)] is measured for several substrates, including propene, 2-butene, cyclohexene, and cis-beta-methylstyrene (CBMS), for catalysis by CPO or P450 isozymes, e.g. oxidation reactions of cyclohexene with compound I. The AOS varies according to substrate and enzyme, on average, epoxidation is slightly favored. The substrates studied lack strongly orienting interactions with residues of the distal binding pocket, consequently, the intrinsic reactivity of the heme-thiolate group with these substrates may make a significant contribution, perhaps the dominant one, to the AOS of P450 and CPO toward them	Leptoxyphium fumago	?	-	-
RH + chloride + H2O2	-	Leptoxyphium fumago	RCl + 2 H2O	-	?

Synonyms

Synonyms	Comment	Organism
chloroperoxidase	-	Leptoxyphium fumago
CPO	-	Leptoxyphium fumago

Cofactor

Cofactor	Comment	Organism	Structure
heme	-	Leptoxyphium fumago

General Information

General Information	Comment	Organism
additional information	substrate specificity via hybrid quantum mechanics/molecular mechanics (QM/MM) calculation and simulation, modeling and structure-function analysis, overview. The influence of the NH-S hydrogen bonds on the full reaction profiles for hydroxylation and epoxidation has been studied by density functional theory (DFT) calculations on small heme-thiolate models that incorporate ammonia molecules hydrogen bonded to a proximal SH- group. The proximal pocket is the key determinant of alkene oxidation selectivity. The selectivity for epoxidation can be rationalized in terms of the proximal pocket's modulation of the thiolate's electron push and consequent influence on the heme redox potential and the basicity of the trans ligand. Creation of two active-site models for each substrate/enzyme combination, one with a bare heme-thiolate and one that also includes the proximal pocket, so that comparison of the PES's reveals the influence of the proximal pocket on the intrinsic reactivity	Leptoxyphium fumago

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Release 2023.1 (January 2023)