Practical Olefin Aziridination with a Broad Substrate Scope

Abstract

The present study illustrates the possibility of a rational approach that bypasses the requirement for stoichiometric amounts of toxic oxidants and metal additives (including reagents and catalysts) in organic redox reactions. We describe an aziridination process that delivers a nitrene functionality to olefins from a readily available N-aminophthalimide. Remarkably, both electron-rich and electron-poor olefins are converted to aziridines with high efficiency. The continuum of applied potentials and the heterogeneous nature of reactions at electrode surfaces allow for the electrochemical discrimination of substrates which have similar redox potentials and therefore cannot be selectively reduced or oxidized using soluble reagents. This selectivity is due to the phenomenon of overpotential, the kinetic inhibition of electron transfer on a particular electrode surface.

Convergent Paired Electrolysis for the Three‐Component Synthesis of Protected Homoallylic Alcohols

“…[1] The problems associated with the use of stoichiometric ammounts of expensive and/or toxic reagents, can be diminished by electrochemical regeneration of the spent reagent, which is used in catalytic amounts. [2] In addition, there are tendencies towards a direct electrochemical transformation of the starting materials so that the expensive and/or toxic reagents are completely substituted.…”

Elektrifizierung der organischen Synthese

“…[139] Yudin and co-workers synthesized aziridines from N-aminophthalimides under potentiostatic control with asilver wire as apseudo-reference electrode (Scheme 48). [140] Thee lectrolysis had to be conducted in ad ivided cell as olefin reduction occurred as as ide reaction when an undivided cell was used. This approach was further developed into an interesting method for the amination of sulfoxides in two subsequent electrolysis processes in divided cells,w ith ap otentiostatic anodic oxidation followed by constantcurrent cathodic reduction.…”

“…Potentiostaticaziridine synthesis with N-aminophthalamide. [140] Scheme 49. Percarbonate-or persulfate-mediated epoxidation.…”

Three‐Membered Heterocycles. Structure and Reactivity

“…The hypervalent iodine reagent can also be generated in situ by combining equimolar amounts of p-iodoanisole and m-chloroperbenzoic acid (entry 2) with no negative impact on yield [76]. An even more atom-economical approach can be realized using electrochemical conditions (entry 3), a stereospecific process that has been described as a click preparation of aziridines [77], and which may proceed via a nitrene intermediate [78][79][80]. A similarly efficient oxidation has been reported using superoxide ion [81].…”