Sodium-iodoxybenzoate mediated highly chemoselective aziridination of olefins

Oxidative aminoaziridination: past, present, and future

“…5,8 Oxidation of API by a 5-valent iodine compound -sodium 2-iodoxybenzoate 13 (IBX, Scheme 7) allows for widening the scope of accessible N-phthalimidoaziridines from both electron-rich and electron-deficient substrates. 23 A noteworthy fact is that the latter compounds not only give the best yields of aziridines, but are also more active in competitive reactions. This sharp distinction between IBX and both LTA and PIDA points out different reactive intermediates.…”

“…24 It is necessary to mention that in the absence of API many unsaturated substrates are oxidized by this reagent (cinnamic alcohol to cinnamic aldehyde etc.). 23 Oxidative aminoaziridination with IBX is chemoselective. Thus the reaction with geraniol proceeded at the C 2 =C 3 bond only, which is in the allylic position to the OH group, and left the C 6 =C 7 bond unaffected.…”

“…Thus the reaction with geraniol proceeded at the C 2 =C 3 bond only, which is in the allylic position to the OH group, and left the C 6 =C 7 bond unaffected. 23 The use of IBX is notable for high yields (about 75%) of API adducts with nonconjugated monosubstituted -СН=СН 2 bonds. 23 At the same time the oxidative aminoaziridination with hypervalent iodine reagents usually proceeds far slower than with LTA and needs tens of hours to reach completion at room temperature and even in the boiling ethyl acetate (77 °С).…”

3-Arylaziridine-2-carboxylic Acid Derivatives and (3-Arylaziridin-2-yl)ketones: The Aziridination Approaches

“…An interesting and perspective oxidant in oxidative aziridination is sodium 2-iodoxybenzoate 36 generated from o -iodoxybenzoic acid (IBX) and Na 2 CO 3 ( Scheme 34 ) [ 117 ]. Various type 29 substrates including unsaturated ketones 29c and amides 29b has been successfully aziridinated to obtain trans - 1b, c type products in 65–92% yields (five examples).…”

Site-Selective, Catalyst-Controlled Alkene Aziridination

“…The rare examples of selective aziridinations in precursors that contain multiple sites of unsaturation typically utilize large differences between the electronic features of the two alkenes to bias reactivity for the more electron-rich alkene. [8][9][10][11][12] Our group has had an ongoing interest in identifying opportunities to harness several unusual features of silvercatalyzed nitrene transfer to achieve tunable, chemo-, siteand stereoselective amination reactions. [13][14][15] Most notably, we found that Ag(I) complexes competent for nitrene trans-fer are able to accommodate a diverse range of coordination geometries.…”