One-Pot Stereoselective Synthesis of anti 3-Alkyl and 3-Aryl-N-p-tosyl-aziridine-2-ketones and 3-Aryl-N-p-tosyl-aziridine-2-carboxylates.

Chen, Dianjun; Timmons, Cody; Guo, Li; Xu, Xin; Li, Guigen

doi:10.1002/chin.200511121

Cited by 5 publications

(7 citation statements)

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“…1,2-Haloamines are important building blocks in organic, bioorganic and medicinal chemistry [1][2][3][4][5][6][7], which can be converted to aziridines [8][9], dehydroamino acids [10] and other compounds [2][3][4][5][6][7] via intra and intermolecular substitution reactions. 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.…”

Section: Discussionmentioning

confidence: 99%

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

Fang

Zhi

Wei

2015

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialAd ry vial wasc harged with (E)-1-(4-methylphenyl)-2-nitropropene( 177m g),b enzamide (242 mg), K 2 CO 3 (454 mg), Ni(OAc) 2 (35 mg),4Åm olecular sieves (500 mg), N-chlorosuccinimide (400mg, 3.0mmol) and CH 2 Cl 2 (5.0ml) with nitrogen atmosphere. The resulting mixturewas stirred at room temperature for 48h and the reaction was then quenched with saturated aqueous Na 2 SO 3 (5.0 mL) solution. The precipitates were filtered offa nd washed with ethylacetate (3´10 ml). The combined organic phases were washed with brine and dried with anhydrous sodium sulfate. 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. 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. So, we synthesized the title compound as apart of this study in order to elucidate the conformation and configuration of this product. The bond lengths and an-gles in the title structure are in good agree with expected values [15].T he dihedral angle betweent he O1-N1-O2 plane and the C4C9 benzene ring is 43.2(2)°. While the dihedral angle between the O3-N2-O4 plane and the C6-C11 benzene ring is 38.4(3)°. For 1-(2-chloro-1-(4-chlorophenyl)-2-nitro-propyl)pyrrolidine-2,5-dione [16], the torsion angles are significantly different.

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Section: Discussionmentioning

confidence: 99%

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

Fang

Zhi

Wei

2015

Zeitschrift Für Kristallographie - New Crystal Structures

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“…N, N-dihalogene- p -toluenesulfonamides are reported as nitrogen sources for both catalytic [ 125 , 126 ] and non-catalytic [ 127 ] aziridinations of cinnamates, cinnamyl amides and chalcone type substrates 29a , c , d ( Scheme 41 ). Interestingly, aziridination with TsNCl 2 was demonstrated as a two-step addition-cyclization process [ 125 , 126 ] via isolable intermediate 40 , but the reaction with TsNBr 2 was reported in a one-step nitrene transfer process [ 127 ]. The specific use of similar aziridinating agent PhSO 2 NBr 2 under Lu(OTf) 3 /chiral ligand catalysis for complex tricyclic aziridine synthesis was noted [ 128 ].…”

Section: Aziridination Of Olefins (Path B)mentioning

confidence: 99%

3-Arylaziridine-2-carboxylic Acid Derivatives and (3-Arylaziridin-2-yl)ketones: The Aziridination Approaches

Strumfs

Uljanovs

Velikijs

et al. 2021

IJMS

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Aziridination reactions represent a powerful tool in aziridine synthesis. Significant progress has been achieved in this field in the last decades, whereas highly functionalized aziridines including 3-arylated aziridine-2-carbonyl compounds play an important role in both medical and synthetic chemistry. For the reasons listed, in the current review we have focused on the ways to obtain 3-arylated aziridines and on the recent advances (mainly since the year 2000) in the methodology of the synthesis of these compounds via aziridination.

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“…The resulting vicinal chloroamino nitriles have great potential applications in pharmaceutical chemistry (40). The vicinal chloroamines have also been reported to be able to take place of the intramolecular S N 2 substitution to form the product of aziridines (41). In our continuous work on the aminohalogenation of α , β ‐unsaturated nitriles, we try to synthesize the cyano aziridines with α , β ‐unsaturated nitriles as starting materials by one‐pot synthetic method.…”

Section: Optimizing the Reaction Catalystamentioning

confidence: 99%

“…The first key step is the aminohalogenation reaction of unsaturated nitriles resulting in haloamine product, which involves the formation of aziridinium intermediate (39). Then, the haloamine intermediate undergoes the intramolecular S N 2 substitution and elimination of chlorine atom in the presence of base (41) to form the final aziridine product.…”

mentioning

confidence: 99%

One‐Pot Highly Stereoselective Synthesis of Cyano Aziridines via the CuCl‐Catalyzed Aminochlorination of α,β‐Unsaturated Nitriles and Intramolecular S_N2 Substitution

et al. 2010

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An efficient one-pot system has been developed for the synthesis of cyano aziridine by using a,bunsaturated nitriles as the alkene substrates and N,N-dichloro-p-toluenesulfonamide (4-TsNCl 2 ) as the nitrogen source. A good scope of alkene substrates was achieved for this reaction. The one-pot reaction, via aminohalogenation and intramolecular S N 2 substitution, was very convenient to carry out at room temperature without the protection of inert gases. Modest to good yields and excellent have been obtained. This method provides an easy route to the cyano aziridine. The structure of the resulting products has been unambiguously confirmed by X-ray structural analysis.

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One-Pot Stereoselective Synthesis of anti 3-Alkyl and 3-Aryl-N-p-tosyl-aziridine-2-ketones and 3-Aryl-N-p-tosyl-aziridine-2-carboxylates.

Cited by 5 publications

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

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

3-Arylaziridine-2-carboxylic Acid Derivatives and (3-Arylaziridin-2-yl)ketones: The Aziridination Approaches

One‐Pot Highly Stereoselective Synthesis of Cyano Aziridines via the CuCl‐Catalyzed Aminochlorination of α,β‐Unsaturated Nitriles and Intramolecular S_N2 Substitution

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One-Pot Stereoselective Synthesis of anti 3-Alkyl and 3-Aryl-N-p-tosyl-aziridine-2-ketones and 3-Aryl-N-p-tosyl-aziridine-2-carboxylates.

Cited by 5 publications

References 0 publications

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

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

3-Arylaziridine-2-carboxylic Acid Derivatives and (3-Arylaziridin-2-yl)ketones: The Aziridination Approaches

One‐Pot Highly Stereoselective Synthesis of Cyano Aziridines via the CuCl‐Catalyzed Aminochlorination of α,β‐Unsaturated Nitriles and Intramolecular SN2 Substitution

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One‐Pot Highly Stereoselective Synthesis of Cyano Aziridines via the CuCl‐Catalyzed Aminochlorination of α,β‐Unsaturated Nitriles and Intramolecular S_N2 Substitution