Practical Olefin Aziridination with a Broad Substrate Scope Superoxide Dismutase-Based Third-Generation Biosensor for Superoxide Anion Electrochemical Immunoassay Moving into the Fast Lane Characterization and Reactions of Previously Elusive 17- Electron Cations:

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Superoxide Dismutase-Based Third-Generation Biosensor for Superoxide Anion Electrochemical Immunoassay Moving into the Fast Lane Characterization and Reactions of Previously Elusive 17Electron Cations: Electrochemical Oxidations of (C H )Cr(CO) and (C H )Co(CO) in the Presence of [B(C F ) ] Although chemical redox reagents can be highly selective, many produce toxic b y p r o d u c t s . I n c o n t r a s t , electrochemical redox reactions (i.e., reactions involving electron transfer at the surface of an electrode) generate fewer by-products, and selectivity can be achieved by using an appropriate redox potential. The aim of this study was to find an alternative method for the aziridination of olefins, since the s t a n d a r d m e t h o d r e q u i r e s stoichiometric amounts of toxic lead(IV) oxidants. The first approach used catalytic amounts of lead(II) acetate at a potential of +1.60 V (the redox potential of lead(II) acetate). However, it was noted that a large overpotential was required for the direct oxidation of olefins at a platinum electrode, and hence aziridination of olefins could be achieved by direct electrochemical oxidation (i.e., in the absence of lead(II) acetate). The optimum applied potential for the aziridination of cyclohexene was +1.8 V (vs. silver pseudo-reference electrode). A number of other olefins could also be aziridinated, with yields between 42 and 93 %.

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تاریخ انتشار 2002