Recent Development of Regio‐ and Stereoselective Aminohalogenation Reaction of Alkenes

Abstract

This microreview presents the development of the catalytic aminohalogenation of olefins. The olefin substrates include electron‐deficient and functionalized ones, such as α,β‐unsaturated esters, α,β‐unsaturated ketones and α,β‐unsaturated nitriles. In addition, the first asymmetric aminohalogenation by the use of Evans chiral auxiliaries is also discussed. The convincing evidence is provided to support the aziridinium mechanism of aminohalogenation reaction. The applications of this reaction are described by converting vicinal haloamines into other important synthetic building blocks. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Crystal structure of 1-benzamido-2-chloro-1-(4-methylphenyl)-2-nitropropane, C17H17ClN2O3

“…Because the carbon-nitrogen and carbon-halogen bonds can be effectively formed in asingle process [11], the aminohalogenation of a,b-unsaturated functionalized olefins has becomeone of the most efficient method to get 1,2-haloamines derivatives. Several a,bunsaturated functionalized olefins, such as a,b-unsaturated carboxylic esters, ketones, nitriles, methylenecyclopropanes and vinylidenecyclopropanes, have been used as theo lefins substrates of aminohalogenation [11], and in these aminohalogenation processes the substituted sulfonamides were mainly used as nitrogen sources.…”

“…The organic solution was concentrated and purified via flash chromatography with ethylacetateand petroleum ether (v/v,1:4) as the eluent to give the title compound as white solid (225 mg , the aminohalogenation of a,b-unsaturated functionalized olefins has becomeone of the most efficient method to get 1,2-haloamines derivatives. Several a,bunsaturated functionalized olefins, such as a,b-unsaturated carboxylic esters, ketones, nitriles, methylenecyclopropanes and vinylidenecyclopropanes, have been used as theo lefins substrates of aminohalogenation [11], and in these aminohalogenation processes the substituted sulfonamides were mainly used as nitrogen sources. Recently, a,b-unsaturated nitros are also found to be good olefins substrates of aminohalogenation [12][13][14],and many reagents, such as N,N-dichloro-p-tolylsulfonamide, and many others have been used as the halogen /nitrogen sources.…”

“…Recently, a,b-unsaturated nitros are also found to be good olefins substrates of aminohalogenation [12][13][14],and many reagents, such as N,N-dichloro-p-tolylsulfonamide, and many others have been used as the halogen /nitrogen sources. Interestingly, in the aminohalogenation of a,b-unsaturated nitros,the amino functionality is added onto the b-position of nitro group and the halo functionality is added onto the a-position, while the amino functionality is normally added onto the aposition and the halo functionality is added onto the b-position of the substrates connecting groups such as ester, ketone or nitrile [11].I nt he compound N-(2-chloro-2-nitro-1-phenylpropyl)-4-methylbenzene-sulfonamide, the a-carbon of the substrate was fully chlorinated [12]. However, the aminohalogenation reactions of (E)-1-(4-methylphenyl)-2-nitro-propene with combination of N-chlorosuccinimide and aryl formamides as nitrogen / halogen sources was not been well documented.…”

Crystal structure of 1-(2-chloro-1-(4-chlorophenyl)-2- nitropropyl)pyrrolidine-2,5-dione, C13H12Cl2N2O4

“…In recent years, many new aminohalogenation processes for several kinds of functionalized alkenes have been developed, with the different nitrogen/halogen sources in the presence of metallic catalysts [3][4][5]. However, the aminohalogenation reactions of (E)-1-(4-chlorophenyl)-2-nitro-propene with N-chloro-succinimide as nitrogen/halogen sources was not been well documented.…”

Unexpected reaction of N,N-dichloroarenesulfonamides with divinyl sulfide: formation of N-[2-chloro- and N-[2,2-dichloro-1-(arylsulfonylamino)ethyl]arenesulfonamides

“…Reaction of N,Ndichlorosulfonamides with alkenes is an efficient method for the synthesis of N-(-chloroalkyl)sulfonamides [9][10][11][12][13] and N-sulfonylpolyhaloaldimines [14][15][16][17][18][19] which were used as key reagents in further preparation of a large range of heterocyclic and open chained functionally substituted sulfonamide derivatives. 10,[14][15][16][17][18][19][24][25][26][27] In elemento-organic chemistry oxidative imination of heteroatomic compounds, and mainly sulfur containing reagents, are of great significance. 1,2,[20][21][22] Divinyl sulfide is an important representative of practically useful sulfur organic compounds.…”