Enzymatic Halogenation and Dehalogenation Reactions: Pervasive and Mechanistically Diverse

Structural Perspective on Enzymatic Halogenation

Simple halogen substituents frequently afford key structural features that account for the potency and selectivity of natural products, including antibiotics and hormones. For example, when a single chlorine atom on the antibiotic vancomycin is replaced by hydrogen, the resulting antibacterial activity decreases by up to 70% ( Harris , C. M. ; Kannan , R. ; Kopecka , H. ; Harris , T. M. J. Am. ...

Insights into enzymatic halogenation from computational studies

The halogenases are a group of enzymes that have only come to the fore over the last 10 years thanks to the discovery and characterization of several novel representatives. They have revealed the fascinating variety of distinct chemical mechanisms that nature utilizes to activate halogens and introduce them into organic substrates. Computational studies using a range of approaches have already ...

Enzymatic dehalogenation of certain brominated and chlorinated compounds.

The dehalogenation in vivo of brominated aliphatic hydrocarbons such as methyl bromide (1) and bromochloromethane (2) has been demonstrated by recovery of inorganic bromide from blood and urine. The intracellular formation of bromide and methyl alcohol from methyl bromide has been advanced as an explanation for its prolonged toxic effect (3). Evidence for the splitting of chlorinated aliphatic ...

Mechanism of the inhibition of enzymatic halogenation by antithyroid agents.

Enzymatic Reactions

It has been argued that a substrate-induced conformational change involving the orientation of catalytic groups cannot affect the specificity for two substrates in an enzymatic system where the chemical step is rate limiting, because such an induced fit would alter the catalytic efficiency for both to an equal extent. To the contrary, the generalized induced-fit treatment described here shows t...