Enzymatic Chemistry of Cyclopropane, Epoxide, and Aziridine Biosynthesis

Oxidative Tailoring Reactions Catalyzed by Nonheme Iron-Dependent Enzymes

“…Any of these could, in principle, abstract a hydrogen atom from the substrate, although kinetic isotope effect studies indicate that it is most likely to be the Fe(III)-superoxide species. The resulting radical intermediate would then collapse to form fosfomycin, after reduction and dehydration of the Fe(III)-hydroperoxide that arises from hydrogen abstraction by Fe(III)-superoxide (Higgins et al, 2005;Thibodeaux, Chang, & Liu, 2012).…”

Direct Stereospecific Synthesis of Unprotected N-H and N-Me Aziridines from Olefins

“…(1–6) The aziridine structural motif, predominantly N-H and to a lesser extent N-alkyl, also appears in biologically active natural products (e.g., azinomycins and mitomycins). (7–9) As a result, the synthesis and chemistry of aziridines have been the subject of intense research during the past 25 years, resulting in multiple aziridination methods. (10–23) The majority of these methods rely either on the transfer of substituted nitrenes, which are generated using strong external oxidants, to the C=C bond of olefins or the transfer of substituted carbenes to the C=N bond of imines.…”

Gold‐Catalyzed Intermolecular Anti‐Markovnikov Hydroamination of Alkylidenecyclopropanes

“…[1] Alkylidenecyclopropanes (ACPs) represent attractive substrates for the synthesis of functionalized cyclopropanes owing to the strain-driven reactivity [2][3][4] and synthetic accessibility [5,6] of ACPs. Indeed, ACPs have been employed widely as building blocks in organic synthesis, [6][7][8] and in this context, transition-metal-catalyzed methods have attracted particular attention.…”