52750-95-5Relevant academic research and scientific papers
Transition state analysis of model and enzymatic prenylation reactions
Lenevich, Stepan,Xu, Juhua,Hosokawa, Ayako,Cramer, Christopher J.,Distefano, Mark D.
, p. 5796 - 5797 (2008/02/04)
To obtain a transition state (TS) structure for an enzyme-catalyzed prenylation reaction, SN1 and SN2 model substitution reactions with dimethylallyl chloride were first studied. 13C Kinetic isotope effects (KIEs) for the model reactions were measured by a natural abundance NMR method and used to validate the computational methods that would be used in the subsequent determination of the enzymatic TS structure. Using a primary 13C KIE and a secondary 2H KIE measured via mass spectrometry, a TS structure for the enzyme-catalyzed reaction was computed; a density functional level of electronic structure theory using the mPW1N functional in combination with the 6-31+G(d) basis set was employed for those calculations. That structure has a C-O bond length of 1.69 A and a C-S bond length of 3.70 A. While the former bond length is similar to that for a nonenzymatic SN2 reaction, the latter is considerably (0.90 A) longer, indicating that the enzyme effects catalysis via an "exploded" TS structure. Copyright
Insecticidal perhaloalkylvinylcyclopropanecarboxylates
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, (2008/06/13)
Perhaloalkylvinylcyclopropanecarboxylates having the general formula STR1 are disclosed wherein one of Y and Z is a perhaloalkyl group. Compounds in which R is hydroxy, halogen or lower alkoxy are novel intermediates for preparation of insecticidal esters in which R is --OR1 where R1 is a wide variety of alcohol residues. The insecticidal efficacy and preparation of the compounds and intermediates therefor are described and exemplified.
