- HKUST-1 Metal Organic Framework as an Efficient Dual-Function Catalyst: Aziridination and One-Pot Ring-Opening Transformation for Formation of β-Aryl Sulfonamides with C-C, C-N, C-S, and C-O Bonds
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Metal-organic frameworks (MOFs) are extensively used in catalysis due to their robust structure, well-defined periodic reaction centers, and high porosity. We report Cu3(BTC)2·(H2O)3 (HKUST-1) as an efficient heterogeneous catalyst for aziridination of al
- Sharma, Debesh,Rasaily, Sagarmani,Pradhan, Sajan,Baruah, Khanindram,Tamang, Sudarsan,Pariyar, Anand
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supporting information
p. 7794 - 7802
(2021/05/26)
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- Make It Green: Copper-Catalyzed Olefin Aziridination in Water with an Iminoiodonane
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The copper complex Tp(CF3)2,BrCu(NCMe) efficiently catalyses the aziridination of olefins in water using PhI=NTs as the nitrene source, with identical activity than that observed when using dichloromethane as the solvent, under the same experim
- Borrego, Elena,Pérez, Pedro J.,Caballero, Ana
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p. 5091 - 5095
(2021/12/09)
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- Is the Electrophilicity of the Metal Nitrene the Sole Predictor of Metal-Mediated Nitrene Transfer to Olefins? Secondary Contributing Factors as Revealed by a Library of High-Spin Co(II) Reagents
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Recent research has highlighted the key role played by the electron affinity of the active metal-nitrene/imido oxidant as the driving force in nitrene additions to olefins to afford valuable aziridines. The present work showcases a library of Co(II) reage
- Kalra, Anshika,Bagchi, Vivek,Paraskevopoulou, Patrina,Das, Purak,Ai, Lin,Sanakis, Yiannis,Raptopoulos, Grigorios,Mohapatra, Sudip,Choudhury, Amitava,Sun, Zhicheng,Cundari, Thomas R.,Stavropoulos, Pericles
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p. 1974 - 1996
(2021/06/28)
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- Expedient Synthesis of 2-Iminothiazolidines via Telescoping Reactions Including Iron-Catalyzed Nitrene Transfer and Domino Ring-Opening Cyclization (DROC)
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2-iminothiazolidines are important scaffold for pharmaceutical drugs. Herein, we describe a fast and easy procedure for their synthesis by a telescoping reaction integrating an iron-catalyzed nitrene transfer under mild conditions. The aziridination react
- Coin, Guillaume,de Ferrier de Montal, Oriane,Dubourdeaux, Patrick,Latour, Jean-Marc
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p. 443 - 448
(2020/12/11)
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- Iron(ii)-catalyzed intermolecular aziridination of alkenes employing hydroxylamine derivatives as clean nitrene sources
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The iron-catalyzed intermolecular aziridination of alkenes with hydroxylamine derivatives is described. Using simple iron(ii) sources and readily available ligands, the formal (2 + 1) cycloaddition process proved to be efficient on both styrenes and aliphatic alkenes, providing access to a wide range of aziridines. In these particularly sustainable reaction conditions, yields up to 89% could be obtained, with a catalyst loading which could be lowered to 5 mol% when the reaction was performed on large scale. Preliminary mechanistic studies suggest that both concerted and stepwise pathways are operating in this transformation. This journal is
- Berhal, Farouk,Grimaud, Laurence,Kirby, Georgina,Prestat, Guillaume,Vitale, Maxime R.
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p. 9428 - 9432
(2021/12/09)
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- Manganese-catalyzed aziridination of olefins with chloramine-T in water and buffered aqueous solutions
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A water-soluble, manganese-porphyrin complex was used to catalytically generate aziridines from olefins in moderate to good yields (up to 93%) upon optimization at room temperature and in aqueous media. Reactions using chloramine-T at slightly acidic to n
- Wolgemuth, Daniel K.,Elmore, Sydnee D.,Cope, James D.,Sheridan, Patrick E.,Stokes, Sean L.,Emerson, Joseph P.
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- Merging Photoredox/Nickel Catalysis for Cross-Electrophile Coupling of Aziridines with Pyridin-1-ium Salts via Dearomatization
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Merging photoredox/nickel catalysis enabling the cross-electrophile coupling of aziridines with pyridin-1-ium salts involving dearomatization for the synthesis of β-(1,4-dihydropyridin-4-yl)-ethylamines, especially including bioactive motif-based analogue
- Xu, Chong-Hui,Li, Jin-Heng,Xiang, Jian-Nan,Deng, Wei
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supporting information
p. 3696 - 3700
(2021/05/04)
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- Transition-Metal-Free Stereospecific Oxidative Annulative Coupling of Indolines with Aziridines
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Tandem C-N bond formation for the oxidative annulation of indolines with aziridines is accomplished employing the combination of DDQ and NaOCl at ambient conditions. Optically active aziridine can be coupled with high enantiomeric purity (>99% ee). The substrate scope, stereocontrol with the enantioenriched substrate, and scale-up are the important practical advantages.
- Karjee, Pallab,Sarkar, Tanumay,Kar, Subhradeep,Punniyamurthy, Tharmalingam
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p. 8261 - 8270
(2020/07/25)
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- Metal-free cascade reactions of aziridines with arylalkynes and aryldiazoniums: Facile access to arylazopyrrolines
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A novel and facile approach to synthesize arylazopyrroline scaffolds via metal-free cascade reactions of aziridines with arylalkynes and aryldiazoniums has been developed, providing access to a variety of 4-arylazo-2-pyrrolines in a highly concise fashion. This efficient process, which can be performed at the gram scale, enjoys operational simplicity and mild and metal-free conditions.
- Rong, Jing,Jiang, Hao,Wang, Sijing,Su, Zhenni,Wang, Huiyan,Tao, Chuanzhou
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supporting information
p. 3149 - 3157
(2020/05/08)
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- First Sustainable Aziridination of Olefins Using Recyclable Copper-Immobilized Magnetic Nanoparticles
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The first copper-catalyzed aziridination of olefins using recyclable magnetic nanoparticles is described. Magnetic nanoparticles were modified with dopamine and used as a support to coordinate copper. The methodology was optimized with styrene as olefin a
- Khodadadi, Mohamad Reza,Pourceau, Gwladys,Becuwe, Matthieu,Wadouachi, Anne,Toumieux, Sylvestre
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supporting information
p. 563 - 566
(2019/03/08)
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- Organocatalytic Olefin Aziridination via Iminium-Catalyzed Nitrene Transfer: Scope, Limitations, and Mechanistic Insight
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Olefin aziridination via organocatalytic nitrene transfer offers potential complementarity to metal-catalyzed methods; however there is a lack of reports of such reactions in the literature. Herein is reported a method that employs an iminium salt to cata
- Johnson, Shea L.,Hilinski, Michael K.
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p. 8589 - 8595
(2019/07/03)
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- Cycloaddition of α-Diazocarbonyl Compounds and N-Tosylaziridines: Synthesis of Polysubstituted 2 H-1,4-Oxazines through Synergetic Catalysis of AgOTf/Cu(OAc)2
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An impressive and new [3 + 3]-cycloaddition of α-diazocarbonyl compounds with N-tosylaziridines via synergetic catalysis of AgOTf and Cu(OAc)2 has been well described, which offers efficient access to highly substituted 2H-1,4-oxazine derivatives. A variety of α-diazocarbonyl compounds and N-tosylaziridines were compatible substrates with convenient operations under mild reaction conditions.
- Fang, Shangwen,Zhao, Yanwei,Li, Haiyan,Zheng, Yonggao,Lian, Pengcheng,Wan, Xiaobing
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supporting information
p. 2356 - 2359
(2019/03/29)
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- Oxidative Dehydrogenative [3+3] Annulation of Benzylhydrazines with Aziridines Leading to Tetrahydrotriazines
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Oxidative dehydrogenative [3+3] annulation of benzylhydrazines with N-sulfonylaziridines is described. A series of complex tetrahydro-1,2,4-triazines were produced under mild reaction conditions.
- Li, Haitao,Liang, Jia,Huo, Congde
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supporting information
p. 878 - 882
(2019/07/18)
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- Photo-induced aziridination of alkenes with N-sulfonyliminoiodinanes
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Activation of N-sulfonyliminiodinanes was achieved by photo-irradiation at 375nm, which enabled the reaction with several alkenes to afford the corresponding aziridines. Mechanistic studies suggested that the reaction would proceed through a stepwise mech
- Masakado, Sota,Kobayashi, Yusuke,Takemoto, Yoshiji
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p. 688 - 690
(2018/06/11)
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- Branched Amine Synthesis via Aziridine or Azetidine Opening with Organotrifluoroborates by Cooperative Br?nsted/Lewis Acid Catalysis: An Acid-Dependent Divergent Mechanism
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A practical catalytic method to synthesize β,β- and γ,γ-substituted amines by opening aziridines and azetidines, respectively, using alkenyl, alkynyl, or aryl/heteroaryl trifluoroborate salts is described. This reaction features simple open-flask reaction conditions, the use of transition-metal-free catalysis, complete regioselectivity, and high diastereoselectivity. Preliminary mechanistic studies suggest that carbocation formation is disfavored. Stereoretentive addition is favored with Br?nsted acid present, while stereoinversion is favored in its absence, indicating divergent mechanisms.
- Nguyen, Truong N.,May, Jeremy A.
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supporting information
p. 3618 - 3621
(2018/06/26)
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- Copper-Catalyzed Aziridination with Redox-Active Ligands: Molecular Spin Catalysis
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Small-molecule catalysts as mimics of biological systems illustrate the chemists’ attempts at emulating the tantalizing abilities displayed by nature's metalloenzymes. Among these innate behaviors, spin multistate reactivity is used by biological systems as it offers thermodynamic leverage towards challenging chemical reactivity but this concept is difficult to translate into the realm of synthetic organometallic catalysis. Here, we report a rare example of molecular spin catalysis involving multistate reactivity in a small-molecule biomimetic copper catalyst applied to aziridination. This behavior is supported by spin state flexibility enabled by the redox-active ligand.
- Ren, Yufeng,Cheaib, Khaled,Jacquet, Jérémy,Vezin, Hervé,Fensterbank, Louis,Orio, Maylis,Blanchard, Sébastien,Desage-El Murr, Marine
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supporting information
p. 5086 - 5090
(2018/02/21)
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- Synthesis of 3,4-diarylsubstituted hexahydro-1H-indoles
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Efficient syntheses of 3,4-diarylsubstituted hexahydro-1H-indoles in good yields with excellent diastereoselectivities were achieved with a two-step protocol comprising an allylic cation mediated nucleophilic addition and an intramolecular cyclization rea
- Zhou, Feilong,Zhao, Erbao,Yan, Ziqin,Chen, Deheng,Zhao, Yujun
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supporting information
p. 1871 - 1874
(2018/04/14)
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- Synthesis of indolines: Via a palladium/norbornene-catalyzed reaction of aziridines with aryl iodides
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A Pd- and norbornene-catalyzed domino procedure has been developed to synthesize indoline compounds. This reaction provides efficient access to indolines by employing aryl iodides with aziridines as new electrophiles. The transformation is scalable and tolerates a range of functional groups.
- Liu, Ce,Liang, Yujie,Zheng, Nian,Zhang, Bo-Sheng,Feng, Yuan,Bi, Siwei,Liang, Yong-Min
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supporting information
p. 3407 - 3410
(2018/04/05)
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- Nickel(II)-Catalyzed [8 + 3]-Cycloaddition of 2-Aryl- N-tosylaziridines with Tropone
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The Ni-catalyzed [8 + 3]-cycloaddition of tropone with 2-aryl-N-tosylaziridines proceeded smoothly under mild reaction conditions, affording various 4-tosyl-2,3,4,4a-tetrahydrocyclohepta[b][1,4]oxazine derivatives in moderate to excellent yields.
- Liu, Honglei,Jia, Hao,Shi, Wangyu,Wang, Chang,Zhang, Cheng,Guo, Hongchao
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supporting information
p. 3570 - 3573
(2018/06/26)
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- Stereospecific Ring Opening and Cycloisomerization of Aziridines with Propargylamines: Synthesis of Functionalized Piperazines and Tetrahydropyrazines
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Stereospecific Cu-catalyzed nucleophilic ring opening of N-sulfonylaziridines with propargylamines and subsequent hydroamination afford piperazines, which leads to double-bond isomerization to furnish tetrahydropyrazines. Optically active aziridines can be cross-coupled with high enantiomeric purities (>98% ee).
- Das, Bijay Ketan,Pradhan, Sourav,Punniyamurthy, Tharmalingam
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supporting information
p. 4444 - 4448
(2018/08/07)
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- First graphene oxide promoted metal-free nitrene insertion into olefins in water: Towards facile synthesis of activated aziridines
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A facile metal-free graphene oxide (GO)-catalyzed synthesis of tosylaziridines using PhINTs as the nitrene source is reported. The reaction involves nitrene insertion into a variety of styrene/nitrostyrene derivatives in the presence of iodine at room tem
- Shukla, Prashant,Mahata, Suhasini,Sahu, Anjumala,Singh, Manorama,Rai, Vijai K.,Rai, Ankita
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p. 48723 - 48729
(2017/11/06)
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- Wheel-to-rhomboid isomerization as well as nitrene transfer catalysis of ruthenium-thiolate wheels
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A unique ruthenium-thiolate molecular rhomboid (?)-[Ru(SAr)2(CO)2]8, which consists of eight octahedra linked by alternate face- and vertex-sharing, was produced by isomerization of the molecular wheel (○)-[Ru(SAr)2/
- Tso, Ken Chi-Hang,Chan, Sharon Lai-Fung,Huang, Jie-Sheng,Che, Chi-Ming
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supporting information
p. 2419 - 2422
(2017/03/01)
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- Tripodal S-Ligand Complexes of Copper(I) as Catalysts for Alkene Aziridination, Sulfide Sulfimidation, and C-H Amination
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Copper(I) complexes of tris(thioimidazolyl)borates (R′TmR), including [Cu(TmPh)(PR″3)] (R″ = Ph, Cu1; Cy, Cu2) and [Cu(R′TmPh)(PR″3)]+ (R′ = N-methylimidazole; R″ = Ph, Cy) were prepared an
- Lam, Tsz Lung,Tso, Ken Chi-Hang,Cao, Bei,Yang, Chen,Chen, Daqing,Chang, Xiao-Yong,Huang, Jie-Sheng,Che, Chi-Ming
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p. 4253 - 4257
(2017/04/26)
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- Rational design of Fe catalysts for olefin aziridination through DFT-based mechanistic analysis
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Nitrene transfer reactions are increasingly used to access various kinds of amine derivatives but the underlying mechanisms have not been unraveled in most cases. Fe-catalyzed aziridination of alkenes has appeared as a promising route to aziridines which
- Patra, Ranjan,Coin, Guillaume,Castro, Ludovic,Dubourdeaux, Patrick,Clémancey, Martin,Pécaut, Jacques,Lebrun, Colette,Maldivi, Pascale,Latour, Jean-Marc
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p. 4388 - 4400
(2017/10/13)
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- One-Pot Acid-Catalyzed Ring-Opening/Cyclization/Oxidation of Aziridines with N-Tosylhydrazones: Access to 1,2,4-Triazines
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A new, three-step, telescoped reaction sequence for the regioselective conversion of N-tosyl hydrazones and aziridines to 3,6-disubstituted and 3,5,6-trisubstituted 1,2,4-triazines is described. The process involves an efficient nucleophilic ring opening of the aziridine, giving access to a wide range of aminohydrazones, isolated with excellent yields. A “one-pot” procedure, combining the ring opening with a cyclization and an oxidation step, allows the preparation of diversified triazines in good yields.
- Crespin, Lorène,Biancalana, Lorenzo,Morack, Tobias,Blakemore, David C.,Ley, Steven V.
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supporting information
p. 1084 - 1087
(2017/03/15)
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- Stereospecific copper-catalyzed domino ring opening and sp3 C-H functionalization of activated aziridines with N-alkylanilines
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Copper efficiently catalyzed nucleophilic ring opening, sp3 C-H functionalization, and C-N bond formation in the presence of tert-butyl hydroperoxide to afford functionalized imidazolidines starting from N-sulfonylaziridines and Nalkylanilines. The products were obtained in high optical purities (95 → 99% ee) with excellent functional group tolerance.
- Sengoden, Mani,Bhowmick, Abhisikta,Punniyamurthy, Tharmalingam
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supporting information
p. 158 - 161
(2017/11/27)
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- Chiral Cu(salen)-Based Metal-Organic Framework for Heterogeneously Catalyzed Aziridination and Amination of Olefins
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A homochiral 3D porous metal-organic framework was assembled from a chiral dicarboxylic acid-functionalized Cu(salen)-based catalyst and could serve as an efficient heterogeneous catalyst for aziridination and allylic amination of olefins. Besides easy separation and reuse of the catalyst, the chiral framework confinement could impart substrate size selectivity, enhance catalyst activity, and induce product enantioselectivity.
- Liu, Yan,Li, Zijian,Yuan, Guozan,Xia, Qingchun,Yuan, Chen,Cui, Yong
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supporting information
p. 12500 - 12503
(2016/12/26)
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- Achieving regio- and stereo-control in the fluorination of aziridines under acidic conditions
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We developed an efficient fluorination protocol that converts easily accessible aziridines into β-fluoroamines, which are important motifs in biologically active molecules. In contrast with traditional fluorination approaches, DMPU-HF has shown both highe
- Okoromoba, Otome E.,Li, Zhou,Robertson, Nicole,Mashuta, Mark S.,Couto, Uenifer R.,Tormena, Cláudio F.,Xu, Bo,Hammond, Gerald B.
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supporting information
p. 13353 - 13356
(2016/11/18)
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- Generation and Ring Opening of Aziridines in Telescoped Continuous Flow Processes
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A simple method for the preparation of a variety of N-sulfonyl aziridines (10 examples) from 1,2-amino alcohols under continuous flow conditions is described. Using flow based methods, the aziridines can be further ring opened with oxygen, carbon, and hal
- Hsueh, Nathanael,Clarkson, Guy J.,Shipman, Michael
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supporting information
p. 3632 - 3635
(2015/07/28)
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- Metal-free one-pot synthesis of 2-substituted and 2,3-disubstituted morpholines from aziridines
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The metal-free synthesis of 2-substituted and 2,3-disubstituted morpholines through a one-pot strategy is described. A simple and inexpensive ammonium persulfate salt enables the reaction of aziridines with halogenated alcohols to proceed via an SN2-type ring opening followed by cyclization of the resulting haloalkoxy amine.
- Sun, Hongnan,Huang, Binbin,Lin, Run,Yang, Chao,Xia, Wujiong
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supporting information
p. 524 - 529
(2015/06/08)
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- A versatile tripodal Cu(I) reagent for C-N bond construction via nitrene-transfer chemistry: Catalytic perspectives and mechanistic insights on C-H aminations/amidinations and olefin aziridinations
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A CuI catalyst (1), supported by a framework of strongly basic guanidinato moieties, mediates nitrene-transfer from PhI=NR sources to a wide variety of aliphatic hydrocarbons (C-H amination or amidination in the presence of nitriles) and olefins (aziridination). Product profiles are consistent with a stepwise rather than concerted C-N bond formation. Mechanistic investigations with the aid of Hammett plots, kinetic isotope effects, labeled stereochemical probes, and radical traps and clocks allow us to conclude that carboradical intermediates play a major role and are generated by hydrogen-atom abstraction from substrate C-H bonds or initial nitrene-addition to one of the olefinic carbons. Subsequent processes include solvent-caged radical recombination to afford the major amination and aziridination products but also one-electron oxidation of diffusively free carboradicals to generate amidination products due to carbocation participation. Analyses of metal- and ligand-centered events by variable temperature electrospray mass spectrometry, cyclic voltammetry, and electron paramagnetic resonance spectroscopy, coupled with computational studies, indicate that an active, but still elusive, copper-nitrene (S = 1) intermediate initially abstracts a hydrogen atom from, or adds nitrene to, C-H and C=C bonds, respectively, followed by a spin flip and radical rebound to afford intra- and intermolecular C-N containing products.
- Bagchi, Vivek,Paraskevopoulou, Patrina,Das, Purak,Chi, Lingyu,Wang, Qiuwen,Choudhury, Amitava,Mathieson, Jennifer S.,Cronin, Leroy,Pardue, Daniel B.,Cundari, Thomas R.,Mitrikas, George,Sanakis, Yiannis,Stavropoulos, Pericles
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supporting information
p. 11362 - 11381
(2014/09/17)
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- Syntheses of a novel fluorinated trisphosphinoborate ligand and its copper and silver complexes. Catalytic activity toward nitrene transfer reactions
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A novel fluorinated ligand, the anionic PhB(CH2P(p-CF 3C6H4)2)3 (PhBP 3 p-CF3Ph), has been synthesized and characterized, as well as its corresponding thallium, copper
- Arenas, Ismael,Fuentes, M. Angeles,Alvarez, Eleuterio,Diaz, Yolanda,Caballero, Ana,Castillon, Sergio,Perez, Pedro J.
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p. 3991 - 3999
(2014/05/06)
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- Stereoselective Lewis acid mediated (3+2) cycloadditions of N-H- and N-sulfonylaziridines with heterocumulenes
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Alkyl and aryl isothiocyanates and carbodiimides are effective substrates in (3+2) cycloadditions with N-sulfonyl-2-substituted aziridines and 2-phenylaziridine for the synthesis of iminothiazolidines and iminoimidazolidines. Additionally, the stereoselec
- Craig, Robert A.,O'Connor, Nicholas R.,Goldberg, Alexander F. G.,Stoltz, Brian M.
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supporting information
p. 4806 - 4813
(2014/05/06)
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- Aziridination of olefins with bromamine-T in presence of iodine as catalyst
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A strategy for achieving synthesis of aziridine employing iodine catalysed aziridination of alkenes with bromamine-T as nitrene source has been described. Ethyl acetate has been found to be the most suitable solvent and the strategy has been extended to v
- Sharma, Chinta Mani,Kashyap, Bishwapran,Phukan, Prodeep
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p. 750 - 753
(2014/07/07)
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- Metal-free aziridination of styrene derivatives with iminoiodinane catalyzed by a combination of iodine and ammonium iodide
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The metal-free catalytic aziridination of styrene derivatives with N-tosyliminophenyliodinane (PhI=NTs) in the presence of a combination of I 2 and tetrabutylammonium iodide (TBAI) is reported. In situ generated TBAI3 from I2/s
- Kiyokawa, Kensuke,Kosaka, Tomoki,Minakata, Satoshi
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supporting information
p. 4858 - 4861
(2013/10/08)
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- Intermolecular Alkene Aziridination: An Original and Efficient Cu I···CuI Dinuclear Catalyst Deriving from a Phospha-Amidinate Ligand
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Mononuclear and dinuclear CuI complexes 1 and 2 derived from the phospha-amidinate ligands [tBu2P(NSiMe3) 2]- and [Ph2P(NSiMe3) 2]-, respectively, have been
- Nebra, Noel,Lescot, Camille,Dauban, Philippe,Mallet-Ladeira, Sonia,Martin-Vaca, Blanca,Bourissou, Didier
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supporting information
p. 984 - 990
(2013/03/14)
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- Nonheme iron-mediated amination of C(sp3)-H bonds. Quinquepyridine-supported iron-imide/nitrene intermediates by experimental studies and DFT calculations
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The 7-coordinate complex [Fe(qpy)(MeCN)2](ClO4) 2 (1, qpy = 2,2′:6′,2″:6″, 2′′′:6′′′,2′′′′- quinquepyridine) is a highly active nonheme iron catalyst for intra- and intermolecular amination of C(sp3)-H bonds. This complex effectively catalyzes the amination of limiting amounts of not only benzylic and allylic C(sp3)-H bonds of hydrocarbons but also the C(sp3)-H bonds of cyclic alkanes and cycloalkane/linear alkane moieties in sulfamate esters, such as those derived from menthane and steroids cholane and androstane, using PhI=NR or "PhI(OAc)2 + H2NR" [R = Ts (p-toluenesulfonyl), Ns (p-nitrobenzenesulfonyl)] as nitrogen source, with the amination products isolated in up to 93% yield. Iron imide/nitrene intermediates [Fe(qpy)(NR)(X)]n+ (CX, X = NR, solvent, or anion) are proposed in these amination reactions on the basis of experimental studies including ESI-MS analysis, crossover experiments, Hammett plots, and correlation with C-H bond dissociation energies and with support by DFT calculations. Species consistent with the formulations of [Fe(qpy)(NTs)2] 2+ (CNTs) and [Fe(qpy)(NTs)]2+ (C) were detected by high-resolution ESI-MS analysis of the reaction mixture of 1 with PhI=NTs (4 equiv). DFT calculations revealed that the reaction barriers for H-atom abstraction of cyclohexane by the ground state of 7-coordinate C NTs and ground state of C are 15.3 and 14.2 kcal/mol, respectively, in line with the observed high activity of 1 in catalyzing the C-H amination of alkanes under mild conditions.
- Liu, Yungen,Guan, Xiangguo,Wong, Ella Lai-Ming,Liu, Peng,Huang, Jie-Sheng,Che, Chi-Ming
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supporting information
p. 7194 - 7204
(2013/06/27)
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- Nanocrystalline zinc peroxide mediated unprecedented nitrene transfer: An expeditious access to N-tosylaziridines
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An unprecedented zinc peroxide (ZnO2) assisted synthetic strategy is reported for the synthesis of N-tosylaziridines from alkenes by using N-tosyliminotriphenylphosphorane (Ph3PNTs) as a nitrene transfer reagent under mild reaction conditions. The reaction of zinc peroxide with Ph3PNTs yielded a zinc oxaziridine intermediate which subsequently reacts with alkenes to give corresponding N-tosylaziridines in high to excellent yields. The Royal Society of Chemistry 2013.
- Verma, Sanny,Jain, Suman L.
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p. 19830 - 19833
(2013/11/06)
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- Iron(iii) tetrakis(pentafluorophenyl)porpholactone catalyzes nitrogen atom transfer to CC and C-H bonds with organic azides
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We have demonstrated that iron porpholactones could be effective catalysts for nitrogen atom transfer reactions such as aziridination of alkenes and amidation of alkanes using organic azides.
- Liang, Lei,Lv, Hongbin,Yu, Yi,Wang, Peng,Zhang, Jun-Long
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supporting information; experimental part
p. 1457 - 1460
(2012/03/22)
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- Polynuclear copper(I) complexes with chelating bis- and tris-N-heterocyclic carbene ligands: Catalytic activity in nitrene and carbene transfer reactions
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Di- and trinuclear complexes of copper(I) bearing bis- or tris-N-heterocyclic carbene ligands have been prepared and evaluated as catalysts in nitrene transfer reactions from PhI=NTs to unsaturated and saturated substrates (olefin aziridination and C-H bond amidation) and carbene transfer reactions from diazo compounds to olefins. The complexes exhibited moderate-to-high catalytic activity in both processes. The tosylamidation of C-H bonds, previously unreported with a NHC-containing copper catalyst, was promoted by the dinuclear complexes. Polynuclear oligo-NHC-copper complexes catalyse the transfer of carbene or nitrene fragments to unsaturated and saturated substrates. The first example of the tosylamidation of C-H bonds with a catalyst containing the NHCCu core is described. Copyright
- Tubaro, Cristina,Biffis, Andrea,Gava, Riccardo,Scattolin, Elena,Volpe, Andrea,Basato, Marino,Diaz-Requejo, M. Mar,Perez, Pedro J.
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experimental part
p. 1367 - 1372
(2012/04/11)
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- Aziridination of Olefins
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A process for aziridination of olefins using NaIO4/alkali metal bromide/H+/Chloramine-T combination in presence of dipolar aprotic solvent under ambient conditions to obtain aziridines is disclosed.
- -
-
Page/Page column 3; 5
(2012/09/05)
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- Nickel-catalyzed negishi alkylations of styrenyl aziridines
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A nickel-catalyzed cross-coupling reaction between N-sulfonyl aziridines and organozinc reagents is reported. The catalytic system comprises an inexpensive and air-stable Ni(II) source and dimethyl fumarate as ligand. Regioselective synthesis of β-substituted amines is possible under mild and functional-group-tolerant conditions. The stereoselectivity of the reaction is consistent with a stereoconvergent mechanism wherein the sulfonamide directs C-C bond formation.
- Huang, Chung-Yang,Doyle, Abigail G.
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supporting information; experimental part
p. 9541 - 9544
(2012/07/14)
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- A facile noncatalytic pathway for the nitrene transfer process: Expeditious access to aziridines
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A fast and efficient method has been developed for generation of sulfonyl nitrene from N,N-dibromo-p-toluenesulfonamide (TsNBr2) in the presence of a base without any catalyst. This method was applied to produce aziridines from different kinds of olefins within a short time in high yields. The Royal Society of Chemistry.
- Saikia, Indranirekha,Kashyap, Bishwapran,Phukan, Prodeep
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p. 2967 - 2969
(2011/04/24)
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- Ag(I)-catalyzed regioselective ring-opening of N -tosylaziridine and N -tosylazetidine with S -, O -, and N -nucleophiles and tethered dinucleophiles
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[Ag(COD)2]PF6 catalyzes the ring-opening of N-tosylaziridines and -azetidines with alcohols, amines, thiols, and related tethered 1,2-ethane dinucleophiles. Initial rate studies and DFT-based evaluation of stepwise energetics suggest
- Bera, Milan,Pratihar, Sanjay,Roy, Sujit
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supporting information; experimental part
p. 1475 - 1478
(2011/04/27)
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- [FeIII(F20-tpp)Cl] Is an effective catalyst for nitrene transfer reactions and animation of saturated hydrocarbons with sulfonyl and aryl azides as nitrogen source under thermal and microwave-assisted conditions
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[FeIII(F20-tpp)Cl] (F20tpp = meso- tetrakis(pentafluorophenyl)porphyrinato dianion) is an effective catalyst for imido/nitrene insertion reactions using sulfonyl and aryl azides as nitrogen source. Under thermal conditions, aziridination of aryl and alkyl alkenes (16 examples, 60-95% yields), sulfimidation of sulfides (11 examples, 76-96% yields), allylic amidation/amination of α-methylstyrenes (15 examples, 68-83% yields), and amination of saturated C-H bonds including that of cycloalkanes and adamantane (eight examples, 64-80% yields) can be accomplished by using 2 mol % [FeIII(F20- tpp)Cl] as catalyst. Under microwave irradiation conditions, the reaction time of aziridination (four examples), allylic amination (five examples), sulfimidation (two examples), and amination of saturated C-H bonds (three examples) can be reduced by up to 16fold (24-48 versus 1.5-6 h) without significantly affecting the product yield and substrate conversion.
- Liu, Yungen,Che, Chi-Ming
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experimental part
p. 10494 - 10501
(2010/10/21)
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- NaIO4/LiBr-mediated aziridination of olefins using chloramine-T
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A new milder protocol for aziridination of a variety of olefins has been described. The process employs catalytic amount of sodium metaperiodate (NaIO4) as an oxidant and LiBr and chloramine-T as the bromine and nitrogen sources, respectively. Interestingly, the formation of aziridine products in all the cases studied takes place presumably through a process of 1,2-aminobromination of alkenes.
- Karabal, Pratibha U.,Chouthaiwale, Pandurang V.,Shaikh, Tanveer M.,Suryavanshi, Gurunath,Sudalai, Arumugam
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experimental part
p. 6460 - 6462
(2011/01/03)
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- Catalyst-free aziridination and unexpected homologation of aziridines from imines
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Aziridination and unpredicted homologation reaction of N-sulfonylimines were achieved easily with a very simple, rapid and mild procedure through the use of diazomethane without the presence of any catalyst. The method represents an attractive alternative
- Branco, Paula Serio,Raje, Vivek Prabhakar,Dourado, Jorge,Gordo, Joana
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experimental part
p. 2968 - 2974
(2010/09/06)
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- Silver(I)-Diene complexes as versatile catalysts for the C -Arylation of N -Tosylaziridines: Mechanistic insight from in situ diagnostics
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(Figure presented) Silver(I) complex [Ag(diene)2] +Y- (where diene = cyclooctadiene, norbornadiene, and 1,3-cyclohexadiene; Y- = PF6-, BF 4-) efficiently catalyzes the
- Bera, Milan,Roy, Sujit
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experimental part
p. 4402 - 4412
(2010/10/01)
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- Synthesis of copper(I) complexes of N-heterocyclic carbene-phenoxyimine/ amine ligands: Structures of mononuclear copper(II), mixed-valence copper(I)/(II), and copper(II) cluster complexes
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Copper(I) bromide complexes (2a and 2b) of NHC-phenol-imine ligand precursors {3-[(1R,2R)-2-{[1-(3,5-di-tert-butyl-2-hydroxyphenyl)meth-(E)- ylidene] amino}cyclohexyl] -1-iso-propyl-4-phenyl-3H-imidazol-1-ium bromide (1a) and 3-[(1R,2R)-2-{[1-(2-hydroxyphenyl)meth-(E)-ylidene] amino}-cyclohexyl] -1-isopropyl-4-phenyl-3H-imidazol-1-ium bro-mide (1b), respectively} have been prepared. Complexes 2aand 2b exhibit copper coordination only through the carbenecarbon atom (C) and do not spontaneously eliminate HBr togive additional phenoxyimine (NO) bonds, which is attrib-uted to intramolecular hydrogen bonding. Crystallisation of2a and 2b gives 2a-and 2b-, respectively, that contain (C) copper(I) bromide and (NO)2 copper(II) coordination. Com-plex 2b-also exhibits intermolecular CuIBr interactions giv-ingaCu2Br2 bridge that links two molecules of 2b resulting in an ellipse motif. Reduction of the ligand precursor iminegroup of 1a allows synthesis of silver(I) and copper(I) NHC-phenolamine complexes 6 and 7, respectively, that also retainthe phenol hydrogen atom. Attempts to selectively prepare2a-gave a copper(II) complex 9 that exhibits an (NO)2CuIIstructure with pendant imidazolium salt groups. Reaction be-tween the silver(I) bromide derivative of 1a and CuCl2·2H2Ogives a complex derived from a Cu6(O)(OH)4Cl3 core and two(NO) and one (CNO) ligands, respectively. The use of 2a and7 as precatalysts for 1,4-conjugate addition to enones andaziridination of alkenes was studied, showing that, whilstboth catalysts are active, enantioselectivities are low, whichis attributed to the lack of Cu-(NO) coordination. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009.
- Simonovic, Stevan,Whitwood, Adrian C.,Clegg, William,Harrington, Ross W.,Hursthouse, Michael B.,Male, Louise,Douthwaite, Richard E.
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experimental part
p. 1786 - 1795
(2009/09/06)
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- Facile construction of highly functionalized 2-pyrrolines via FeCl 3-catalyzed reaction of aziridines with arylalkynes
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A series of highly functionalized 2-pyrrolines have been constructed by using a novel FeCl3-catalyzed reaction of aziridines with arylalkynes, in which an aryl-substituted alkenyl cation is involved.
- Fan, Jinmin,Gao, Linfeng,Wang, Zhiyong
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supporting information; scheme or table
p. 5021 - 5023
(2010/01/06)
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