Aziridinyl Anions: Generation, Reactivity, and Use in Modern Synthetic Chemistry

Three-component synthesis of highly functionalized aziridines containing a peptide side chain and their one-step transformation into β-functionalized α-ketoamides

“…While the synthetic applications of aziridines have received much attention [11,25–29] there is little precedent of their opening with weak nucleophiles such as carboxylate anions [30]. However, we expected that the presence of the 2-methoxy substituent would facilitate the desired transformation.…”

α,β-Aziridinylphosphonates by lithium amide-induced phosphonyl migration from nitrogen to carbon in terminal aziridines

“…In an attempt to induce greater conversion of 1a with n -BuLi, the amount of the latter was increased to 3 equivalents, however only 25% of 3a was obtained. Given previous successes with the use of lithium amides to deprotonate differently N -protected terminal aziridines [9–14], we moved on to study such bases with N -phosphonate aziridine 1a . Firstly, LDA (lithium diisopropylamid) and LiNCy 2 were examined.…”

“…Aziridinylphosphonates 3 have previously been prepared by a variety of methods [4–6], of which ring-closure following either Sharpless aminohydroxylation of α,β-unsaturated phosphonates [7], or α-halophosphonate addition to sulfinimines [8] constitute notable asymmetric approaches, albeit principally leading to β-aryl substituted α,β-aziridinylphosphonates. Arising from our investigations [9–13] on the generation and subsequent chemistry of α-lithiated terminal aziridines [14], we considered whether α,β-aziridinylphosphonates 3 could be accessed by α-lithiation of N -phosphonate terminal aziridines 1 , followed by N - to C -[1,2]-anionic phosphonyl group migration in lithiated intermediate 2 (Scheme 1). Here, we present full details of this study [15].…”

Synthesis and Purification of Iodoaziridines Involving Quantitative Selection of the Optimal Stationary Phase for Chromatography

“…They display a vast array of reactivity often involving aziridine ring opening 2,3 , particularly as intermediates in the synthesis of functionalized amines 4,5 , or the formation of other nitrogen containing heterocycles 6,7 . The synthesis of a range of aziridine derivatives by functionalization of a precursor containing an intact aziridine ring has emerged as a viable strategy 8 . Functional group-metal exchange, to generate an aziridinyl anion, and reaction with electrophiles has been shown to be effective 9,10,11 , and recently regio-and stereoselective deprotonation of N-protected aziridines has also been achieved [12][13][14][15] .…”