Aziridine Natural Products – Discovery, Biological Activity and Biosynthesis

Enzymatic Chemistry of Cyclopropane, Epoxide, and Aziridine Biosynthesis

“…To date, only a handful of aziridine-containing natural products are known, 237 and the biosynthetic gene clusters for only three of these have been published: the mitomycin ( 4 ) cluster from Streptomyces lavendulae , 238 the azinomycin ( 5 ) cluster from Streptomyces sahachiroi , 239 and the azicemicin ( 8 ) cluster from Kibdelosporangium sp. MJ126-NF4 (see Figure 1 for structures).…”

“…Interestingly, formation of the aziridine ring has been proposed to proceed through an S N 2 mechanism involving nucleophilic displacement of the C-3 hydroxyl group (or its derivative) by the C-2 amino group of the glucosamine moiety (see 179 → 180 in Scheme 31A). 237 …”

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.…”

Three‐Membered Heterocycles. Structure and Reactivity

“…The aziridination is facilitated by substoichiometric quantities of iodine [49] (Table 2.1, entry 13). A conceptually related protocol is carried out using t-butylhypoiodite, prepared in situ from t-butylhypochlorite and sodium iodide [50] (Table 2.1, entry 14). Progress continues to be made in the asymmetric aziridination of olefins using the same general approach (Scheme 2.3), but with chiral catalyst systems ( Table 2.2).…”

“…13 C coupling [13]. Aziridine moieties are imbedded in structurally diverse natural products from various sources (Figure 2.2), and the reader is directed to Lowdens excellent recent treatise on this topic [14]. Isolated from Streptomyces griseofuscus [15,16], azinomycin A (2) and azinomycin B (3, also known as carzinophilin) are among the most intensely studied members of this class [17][18][19].…”