Transition Metal Catalyzed Aziridinations and Amidations

Imidoiodanes and especially A-tosyliminoiodanes, ArINTs (Section 2.1.12.4), have found broad synthetic application as useful nitrene precursors in transition metal catalyzed aziridination of aUcenes and amidation of various organic substrates [584, 761]. Mansuy and coworkers in 1984 first reported the aziridination of alkenes with tosyliminoiodane PhINTs in the presence of iron- or manganese-porphyrins [762]. This reaction has a mechanism similar to the metal-catalyzed oxygen atom transfer reactions of iodosylbenzene (Section 3.1.20) and involves a metal-nitrene complex as the intermediate. 

Various chiral ligands or counter-anions, or complexes of other than copper transition metals, have been evaluated in these reactions. High enantioselectivity in the copper-catalyzed aziridination of styrene derivatives was observed in the presence of chiral biaryldiamines [782], chiral C2-symmetric bisferrocenyldiamines 

Mechanistic studies of copper-catalyzed aziridinations have demonstrated that copper nitrene species are the key intermediates in this reaction [802-804]. 

Mn(TFPP)Cl = chloro[5,10,15,20-tetrakis(pentafluorophenyl)poiphyrinato] manganese(III) 

R = Ph, 4-CIC6H4,4-MeOC6H4. PhCH2,4-CIC6H4CH2,4-MeOC6H4CH2, etc. Ns= 2-NO2C6H4SO2 

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