Aminopyridinium iodide as a NH transferring agent for the synthesis of 2-aroyl-3-aryl aziridines

Abstract

by bromination of the related α,β-unsaturated carbonyl compounds, followed with the reaction of ammonia solution [5][6][7][8][9][10].Another synthetic pathway for the synthesis of aziridinyl ketones involves formation of β-hydroxyamino derivatives followed by treatment with either metal alcoholates, or hydroxylamine hydrochloride and then potassium hydroxide [11][12][13][14]. It has been reported the interaction of unsaturated ketones with N-tosyliminoaryliodinanes in the presence of mono-valent copper complexes produces the related aziridinyl ketone [15,16].It was also reported that oximes could be converted into N-unsubstituted aziridines by treatment with Grignard reagents or by reduction with lithium aluminum hydride in certain cases [17].3,3-Pentamethyleneoxaziridine can transfer its NH group to electron-deficient olefins to give N-unsubstituted aziridines in low yields [17,18]. 2-ketoaziridine starting materials were also prepared using 1,4-addition of methoxyamine to α,β-unsaturated ketones followed by basepromoted ring closure [19]. Ylides are another kind of potential NH transfer agent. Free sulfimides HN = SR 2 , sulfur-nitrogen ylide [20][21][22][23][24], are used for the direct synthesis of N-unsubstituted aziridines. An one step synthesis of aziridine by the type addition off free sulfimide has been reported but yields are unsatisfactory and enaminoketones are obtained as major byproducts in moderate yields.On the other hand, an amineimide, as a type of nitrogennitrogen ylide, is an effective NH source for direct N-unsubstituted aziridination of electron-deficient olefins. Recently, a few method has been reported that tertiary amines such as N-methylmorpholin [25], 1,4-diazabicyclo[2.2.2]octane (DABCO) [26,27]. Quinine chiral tertiary amine [28] and Troger s base [29] can prepare amine imide which reacts with chalcone to give desire aziridinyl ketones (Scheme 1).Abstract A new approach for the synthesis of N-H ketoaziridines is described. 1-aminopyridinium iodide as a NH transferring agent provides a straightforward access to the 2-aroyl-3-arylaziridines from the corresponding 1,3-diarylprop-2-en-1-one. A possible general mechanism involving the N-N ylide is proposed.

Recent advances of aminoazanium salts as amination reagents in organic synthesis

“…In 2015, Samimi reported that another amination reagent 1-aminopyridinium iodide can also carry out the aziridination of chalcone. 11 The proposed mechanism is as follows: the tertiary amine reacted in situ to produce the hydrazinium salt 7 and regenerated as a leaving group; it is believed that the tertiary amine could theoretically act as a catalyst (Scheme 5). In 2006, the Shi group first reported a catalytic process for the synthesis of α-keto aziridines from chalcones.…”

“…In 2015, Samimi reported that another amination reagent 1-aminopyridinium iodide can also carry out the aziridination of chalcone. 11…”