Investigations in the Transition Metal Catalyzed Aziridination of Olefins, Amination, and Other Insertion Reactions with Bromamine-T as the Source of Nitrene

Abstract

Investigations into the transition metal catalyzed aziridination of olefins with Bromamine-T as a new source of nitrene is presented in this account. Comparison of Chloramine-T and Bromamine-T in this reaction indicates that the latter is superior as the source of nitrene. Systematic study with several transition metal based catalysts suggests that Cu-halides are the best catalysts. A first report of aziridination under microwave and ultrasound irradiation conditions is also presented. Copper-catalyzed aziridination of methyl cinnamate with Bromamine-T did not proceed at ambient temperature but was effected smoothly under ultrasound irradiation to furnish trans-aziridine selectively, while under microwave irradiation, a mixture of cis and trans isomers, was obtained. It has been demonstrated that aziridination of olefins proceeds smoothly with inexpensive bleaching powder. Preliminary results of Rh-catalyzed benzylic insertion reactions with Bromamine-T are included in this account.

Iodine Monochloride–Amine Complexes: An Experimental and Computational Approach to New Chiral Electrophiles

“…After stirring for 10 h, the reaction was diluted with H 2 O (50 mL) and extracted with CH 2 Cl 2 (3 30 mL). After evaporation of the solvent and the performance of flash chromatography (silica gel, tert-butylmethyl ether/pentane 1:2), 9 c was obtained quantitatively (1.75 g, 100 % yield For preparation and spectral data, see reference [32].…”

The (Porphyrin)ruthenium‐Catalyzed Aziridination of Olefins Using Aryl Azides as Nitrogen Sources

“…[28][29][30][31] It should be noted that by using these synthetic procedures the side-product of the reaction is iodobenzene, and a sulfonyl group is always introduced into the aminated compound. To overcome some of the limitations associated with the use of iminoiodinane compounds, alternative nitrene sources such as chloramine-T [32][33][34][35] or bromamine-T [36][37][38][39] have been employed. In any case, the N-protecting group is a sulfonyl derivative.…”

Alkane Catalytic Functionalization by Carbene or Nitrene Insertion Reactions

“…Similar derivatives with other substituents in the para position of the arylsulfonyl group have been used for the same purpose [96]. Also chloramine-T (NaClNTs) [97,98] and bromamine-T (NaBrNTs) [99,100] have been tested as the nitrene sources. All those reagents are quite unsoluble in most organic solvents, therefore conditioning the reaction rate of the overall process to their dissolution rate.…”