- Asymmetric aziridination of chalcone promoted by binaphthalene-based chiral amines
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Aminimines derived in situ from a number of enantiomerically pure binaphthalene-based tertiary amines have been used for the asymmetric aziridination of chalcone, providing N-unprotected aziridines with ee values of up to 43%. A chiral hydrazinium salt has been isolated for the first time and shown to provide similar yield and enantioselectivity to the in situ process in reaction with chalcone. Georg Thieme Verlag Stuttgart, New York.
- Page, Philip C. Bulman,Bordogna, Céline,Strutt, Ian,Chan, Yohan,Buckley, Benjamin R.
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- Synthesis of aziridines by electrochemical oxidative annulation of chalcones with primary amines
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Synthesis of aziridines by electrochemical oxidative annulation of chalcone 1,3-diphenyl-2-propen-1-one with primary amines has been developed under external oxidant - and base-free conditions. The reaction constitutes a new transformation of chalcones with primary amines to aziridines, providing a complementary, simple, and environmentally friendly approach to the currently available methods. A reaction mechanism for this transformation has been proposed based on the cyclic voltammetry.
- Gu, Lijun,He, Yonghui,Li, Ganpeng,Zeng, Dongwen,Zhang, Lizhu
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- On-Demand Generation and Use in Continuous Synthesis of the Ambiphilic Nitrogen Source Chloramine
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Herein, we demonstrate the on-demand synthesis of chloramine from aqueous ammonia and sodium hypochlorite solutions, and its subsequent utilization as an ambiphilic nitrogen source in continuous-flow synthesis. Despite its advantages in cost and atom economy, chloramine has not seen widespread use in batch synthesis due to its unstable and hazardous nature. Continuous-flow chemistry, however, provides an excellent platform for generating and handling chloramine in a safe, reliable, and inexpensive manner. Unsaturated aldehydes are converted to valuable aziridines and nitriles, and thioethers are converted to sulfoxides, in moderate to good yields and exceedingly short reaction times. In this telescoped process, chloramine is generated in situ and immediately used, providing safe and efficient conditions for reaction scale-up while mitigating the issue of its decomposition over time.
- Danahy, Kelley E.,Styduhar, Evan D.,Fodness, Aria M.,Heckman, Laurel M.,Jamison, Timothy F.
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supporting information
p. 8392 - 8395
(2020/11/18)
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- Aminopyridinium iodide as a NH transferring agent for the synthesis of 2-aroyl-3-aryl aziridines
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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.
- Samimi, Heshmat A.,Momeni, Ahmad R.
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p. 2221 - 2225
(2015/10/19)
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- Efficient aziridination of α,β-unsaturated ketones with O-(2,4-dinitrophenyl)-hydroxylamine
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The aziridination of α,β-unsaturated ketones with O-(2,4-dinitrophenyl)-hydroxylamine and tertiary amine was developed. trans-Aziridines were obtained exclusively in good yields. The reaction is proposed to occur via an aminimide intermediate. Copyright T
- Wang, Jin-Jia,Lao, Jin-Hua,Li, Xue-Ming,Lu, Rui-Jiong,Miao, Hui,Yan, Ming
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experimental part
p. 1577 - 1584
(2012/05/05)
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- Amine-promoted, organocatalytic aziridination of enones
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(Chemical Equation Presented) A novel method is presented using N-N ylides (prepared by in situ amination of a tertiary amine) for the aziridination of a range of enone systems. The amine may be used sub-stoichiometrically, and promising levels of enantioselectivity are observed with quinine as promoter.
- Armstrong, Alan,Baxter, Carl A.,Lamont, Scott G.,Pape, Andrew R.,Wincewicz, Richard
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p. 351 - 353
(2007/10/03)
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- Facile preparation of allyl amines and pyrazoles by hydrazinolysis of 2-ketoaziridines
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Allyl amines and pyrazoles can be obtained by hydrazinolysis of 2-ketoaziridines. A variety of aziridines, including N-unprotected, N-substituted, as well as bicyclic enamine and aminal type, can be transformed into diversely substituted linear or cyclic products. The hydrazinolysis of homochiral aziridines proceeds without racemization.
- Chen, Gang,Sasaki, Mikio,Yudin, Andrei K.
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p. 255 - 259
(2007/10/03)
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- An amine-promoted aziridination of chalcones
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(Chemical Equation Presented) Without protection: α-Keto aziridines have been formed in a novel amine-promoted direct aziridination of chalcones using an aminimide generated in situ from a tertiary amine and O-mesitylenesulfonylhydroxylamine (MSH) in the
- Shen, Yu-Mei,Zhao, Mei-Xin,Xu, Jiaxi,Shi, Yian
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p. 8005 - 8008
(2007/10/03)
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- N-amino-N-methylmorpholinium salts: Highly active aziridination reagents for chalcones
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A highly effective aziridination reagent, based on N-methylmorpholine, is reported which effects rapid conversion of chalcones to N-unfunctionalised aziridines at room temperature. Georg Thieme Verlag Stuttgart.
- Armstrong, Alan,Carbery, David R.,Lamont, Scott G.,Pape, Andrew R.,Wincewicz, Richard
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p. 2504 - 2506
(2008/02/11)
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- Chiral rare earth metal complex-catalyzed conjugate addition of O-alkylhydroxylamines. An efficient synthetic entry into optically active 2-acyl aziridines
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The conjugate addition of O-alkylhydroxylamines to α,β-unsaturated ketones is effectively catalyzed by chiral rare earth metal complexes to afford the corresponding β-amino ketones with high enantioselectivities (up to 99% ee) in almost quantitative yields, which are, upon treatment with a base catalyst, quantitatively converted into the 2-acyl aziridines without losing their enantiopurities. The protocol is highly practical thus providing an easy access to enantiopure 2-acyl aziridines and their derivatives in good quantities.
- Jin, Xiu Lan,Sugihara, Hiroyasu,Daikai, Kazuhiro,Tateishi, Hiroki,Jin, Yong Zhi,Furuno, Hiroshi,Inanaga, Junji
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p. 8321 - 8329
(2007/10/03)
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- Direct NH-aziridination of α,β-unsaturated ketones
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1-Aryl-α,β-unsaturated ketones were directly aziridinated, N-unsubstituted, in a one-pot reaction with satisfactory yields by N,N′-diamino-1,4-diazoniabicyclo[2.2.2]octane dinitrate, a nitrogen-nitrogen ylide precursor, in the presence of sodium hydride.
- Xu, Jiaxi,Jiao, Peng
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p. 1491 - 1493
(2007/10/03)
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- A novel two-step preparation of enaminoketones by amination of α,β- unsaturated ketones with methoxyamine
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β-Methoxyaminoketones, derived from the addition of methoxyamine to 1,3-diaryl-2-propen-1-one, underwent base-induced β-elimination to furnish the corresponding enaminoketones in good to moderate yields. The reaction conditions and substituents on the substrates significantly influenced the selectivity in the production of enaminoketone and/or aziridineketone.
- Seko, Shinzo,Tani, Nobuhiro
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p. 8117 - 8120
(2007/10/03)
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- Synthesis of 4-phenylpiperidines by tandem Wittig olefination-aza-Wittig rearrangement of 2-benzoylaziridines
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A number of routes to 2-vinylaziridines are reported.N-Alkylation of a range of 2-benzoyl-3-alkylaziridines with tert-butyl bromoacetate followed by Wittig olefination gave directly a range of 4-phenylpiperidines.The intermediate 2-vinylaziridines rearran
- Coldham, Iain,Collis, Alan J.,Mould, Roger J.,Rathmell, Richard E.
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p. 2739 - 2746
(2007/10/02)
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- Ring Expansion of Aziridines to Piperidines using the Aza-Wittig Rearrangement
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A one-pot, two-step synthesis of unsaturated piperidines from 2-keto aziridines is reported.Treatment of a range of 2-keto aziridines with two equivalents of a phosphonium ylide generates intermediate vinyl aziridines which rearrange by a -sigmatropi
- Coldham, Iain,Collis, Alan J.,Mould, Roger J.,Rathmell, Richard E.
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p. 3557 - 3560
(2007/10/02)
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- ONE STEP SYNTHESIS OF AZIRIDINES BY THE MICHAEL TYPE ADDITION OF FREE SULFIMIDES
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The Michael type additions of diphenyl N-unsubstituted sulfimide (free sulfimide) to various electrophilic olefins were carried out.The reaction with cis- and trans-dibenzoylethylene, dimethylfumarate, dimethylmaleate, benzalacetophenone and benzalacetone gave mainly the corresponding trans-2-acylaziridines and trans-enaminoketones.However, phenyl vinyl sulfone or acrylonitrile afforded not the corresponding aziridine but diphenyl-N-2-cyano or N-2-phenylsulfonylethylsulfimide, a simple Michael adduct.When optically active (+)-(R)-o-methoxyphenylphenyl free sulfimide was treated with such an α,β-unsaturated carbonyl compound as benzalacetophenone, an optically active 2-acylaziridine, i.e., (-)-trans-2-benzoyl-3-phenylaziridine was obtained in ca 30percent optical purity and its absolute configuration was assigned as (2R,3S) upon chemical transformation to the configurationally known 2-phenyl-2-benzoylamino-1-ethanol or by comparing its CD spectrum with that of (1R,2R)-1-phenyl-2-benzoyl-cyclopropane.Meanwhile, (-)-(S)-o-methoxyphenylphenyl free sulfimide was found to react with benzalacetophenone to afford (+)-trans-2-benzoyl-3-phenylaziridine of 25percent optical purity.Effects of solvent and temperature on both the distribution of the products ratio and the optical yield were examined.
- Furukawa, Naomichi,Yoshimura, Toshiaki,Ohtsu, Masami,Akasaka, Takeshi,Oae, Shigeru
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- AZIRIDINYL KETONES AND THEIR HETEROANALOGS. 5. SYNTHESIS AND STRUCTURES OF 2-ARYL-3-AROYLAZIRIDINES
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A number of trans- and cis-isomeric 1-R-2-aryl-3-aroylaziridines were synthesized, and their IR spectra were studied.Intramolecular hydrogen bonding is realized in the trans isomers when R = H, and they exist in the only possible conformation (intermediat
- Orlov, V. D.,Yaremenko, F. G.,Lavrushin, V. F.
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p. 1128 - 1133
(2007/10/02)
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