- 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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- Ni-Catalyzed Carboxylation of Aziridines en Route to β-Amino Acids
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A Ni-catalyzed reductive carboxylation of N-substituted aziridines with CO2 at atmospheric pressure is disclosed. The protocol is characterized by its mild conditions, experimental ease, and exquisite chemo- and regioselectivity pattern, thus unlocking a new catalytic blueprint to access β-amino acids, important building blocks with considerable potential as peptidomimetics.
- Davies, Jacob,Janssen-Müller, Daniel,Zimin, Dmitry P.,Day, Craig S.,Yanagi, Tomoyuki,Elfert, Jonas,Martin, Ruben
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supporting information
p. 4949 - 4954
(2021/04/07)
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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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- Synthesis of β-Phenethylamines via Ni/Photoredox Cross-Electrophile Coupling of Aliphatic Aziridines and Aryl Iodides
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A photoassisted Ni-catalyzed reductive cross-coupling between tosyl-protected alkyl aziridines and commercially available (hetero)aryl iodides is reported. This mild and modular method proceeds in the absence of stoichiometric heterogeneous reductants and uses an inexpensive organic photocatalyst to access medicinally valuable β-phenethylamine derivatives. Unprecedented reactivity was achieved with the activation of cyclic aziridines. Mechanistic studies suggest that the regioselectivity and reactivity observed under these conditions are a result of nucleophilic iodide ring opening of the aziridine to generate an iodoamine as the active electrophile. This strategy also enables cross-coupling with Boc-protected aziridines.
- Steiman, Talia J.,Liu, Junyi,Mengiste, Amanuella,Doyle, Abigail G.
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supporting information
p. 7598 - 7605
(2020/04/21)
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- An Electron-Poor Dioxa-[2.1.1]-(2,6)-pyridinophane Ligand and Its Application in Cu-Catalyzed Olefin Aziridination
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A novel macrocyclic 1,7-dioxa-[2.1.1]-(2,6)-pyridinophane ligand has been synthesized and crystallographically characterized. Two derived metal complexes, dichloropalladium(II) and chlorocopper(I), were prepared. In the palladium(II) complex LPdCl2/
- Yang, Fan,Ruan, Jiaheng,Zavalij, Peter Y.,Vedernikov, Andrei N.
-
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- Tandem aziridine ring opening-disulfide formation-reduction-Michael addition in one-pot mediated by tetrathiomolybdate
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Abstract A detailed study of tetrathiomolybdate mediated tandem regio- and stereoselective ring opening of aziridine, disulfide formation, reduction of disulfide bond and Michael reaction in a one-pot operation is reported. This constitutes four reactions
- Sureshkumar, Devarajulu,Gunasundari, Thanikachalam,Chandrasekaran, Srinivasan
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p. 7267 - 7281
(2015/08/24)
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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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- Synthesis of 1,4-benzoxazepine derivatives via a novel domino aziridine ring-opening and isocyanide-insertion reaction
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A novel and efficient domino process has been developed for the synthesis of 1,4-benzoxazepine derivatives from a range of readily accessible N-tosylaziridines, 2-iodophenols and isocyanides. This process involves the aziridine ring-opening reaction with 2-iodophenol, followed by a palladium-catalyzed isocyanide-insertion reaction. This regioselective and high-yielding transformation could be extended to its application for the synthesis of natural products and biologically interesting heterocycles. Copyright
- Ji, Fei,Lv, Mei-Fang,Yi, Wen-Bin,Cai, Chun
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p. 3401 - 3406
(2013/12/04)
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- A rapid and facile method for the general synthesis of 3-aryl substituted 4,5,6,7-tetrahydro[1,2,3]triazolo[1,5-a]pyrazines and their ring fused analogues
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We report a general and facile method that provides rapid entry into 3-aryl substituted 4,5,6,7-tetrahydro[1,2,3]triazolo[1,5-a]pyrazines and their ring fused analogues in one-pot under palladium-copper catalysis. The methodology utilises simple and easily available substrates of broad range. The applicability of this reaction for the synthesis of optically active products has been demonstrated. A plausible reaction mechanism has also been proposed.
- Chowdhury, Chinmay,Mukherjee, Sanjukta,Chakraborty, Biswajit,Achari, Basudeb
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supporting information; scheme or table
p. 5856 - 5862
(2011/09/30)
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- β-Elimination of an aziridine to an allylic amine: A mechanistic study
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The base-induced rearrangement of aziridines has been examined using a combination of calculations and experiment. The calculations show that the substituent on nitrogen is a critical feature that greatly affects the favorability of both α-deprotonation,
- Morgan, Kathleen M.,Brown Jr., Garry,Pichon, Monique A.,Green, Geannette Y.
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experimental part
p. 1144 - 1150
(2012/03/09)
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- Catalyst-free regio- and stereospecific synthesis of β-sulfonamido dithiocarbamates: Efficient ring-opening reactions of N-tosyl aziridines by dialkyldithiocarbamates
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Lord of the ring-opening! A metal-free strategy involving ring-opening of aziridines by the sodium salt of dialkyldithiocarbamate has been employed to give a variety of β-sulfonamido dithiocarbamates. The in situ generation of dialkyldithiocarbamates prov
- Alagiri, Kaliyamoorthy,Prabhu, Kandikere Ramaiah
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supporting information; experimental part
p. 6922 - 6925
(2011/07/08)
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- Palladium-catalyzed domino ring-opening/carboxamidation reactions of N -tosyl aziridines and 2-iodothiophenols: A facile and efficient approach to 1,4-benzothiazepin-5-ones
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A novel and efficient domino procedure has been developed for the synthesis of 1,4-benzothiazepin-5-ones from simple and readily accessible N-tosyl aziridines and o-iodothiophenols. This process involves aziridines ring-opening with o-iodothiophenols, followed by palladium-catalyzed intramolecular carboxamidation. The scope and limitation of this transformation have been investigated in detail by using various aziridines and o-iodothiophenols.
- Zeng, Fanlong,Alper, Howard
-
supporting information; experimental part
p. 5567 - 5569
(2011/02/23)
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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
-
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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- Silver(I)-catalyzed dual activation of propargylic alcohol and aziridine/azetidine: Triggering ring-opening and endo-selective ring-closing in a cascade
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(Chemical Equation Presented) [Ag(COD)2]PF6 catalyzes the reaction between propargyl alcohols and N-tosylaziridines/azetidines leading to a diverse range of N,O-heterocycles, namely, oxazines, oxazepines, and oxazocines via ring-open
- Bera, Milan,Roy, Sujit
-
supporting information; experimental part
p. 8814 - 8817
(2010/03/01)
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- Generation of nitrene by the photolysis of N-substituted iminodibenzothiophene
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(Chemical Equation Presented) To evaluate the ability of dibenzothiophene N-substituted sulfilimines as photochemical nitrene sources, their photolyses in the presence of several trapping reagents, such as sulfides, olefins, and phosphorus compounds, were performed. In the reactions, the corresponding imino-transfer compounds, namely sulfilimines, aziridines, and iminophosphoranes, were formed in good yields, indicating dibenzothiophene N-tosyl and N-acylsulfilimines have a potent nature as nitrogen sources.
- Morita, Hiroyuki,Tatami, Atsushi,Maeda, Tetsuo,Byung, Ju Kim,Kawashima, Wataru,Yoshimura, Toshiaki,Abe, Hitoshi,Akasaka, Takeshi
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scheme or table
p. 7159 - 7163
(2009/04/18)
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- PhI(OAc)2/I2 induced aziridination of alkenes with TsNH2 under mild conditions
-
The aziridination of alkenes with the direct use of p-toluenesulfonamide (TsNH2) was achieved by using PhI(OAc)2 and I2 under mild conditions. The reaction affords aziridines in moderate to good yields, and offers good man
- Fan, Renhua,Pu, Dongming,Gan, Jianhong,Wang, Bing
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p. 4925 - 4928
(2008/09/21)
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- Two-step synthesis of N-sulfonyl aziridines from epoxides
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A convenient and high-yielding two-step synthesis of N-sulfonyl aziridines starting from epoxides is described. The method, which involves epoxide ring opening with sulfonamides and subsequent mesylation-cyclisation, is particularly suitable for variation
- Huang, Jianhui,O'Brien, Peter
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p. 425 - 434
(2007/10/03)
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- A practical, fast, and high-yielding aziridination procedure using simple Cu(II) complexes containing N-donor pyridine-based ligands
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Four-coordinate dichlorocopper(II) complexes derived from di(2-pyridyl)methanes or pyridine itself exhibit high catalytic activity in aziridination of regular olefins with PhINTs in weakly coordinating chloroform in the presence of 1-2 equiv of NaBAr
- Mohr, Fabian,Binfield, Seth A.,Fettinger, James C.,Vedernikov, Andrei N.
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p. 4833 - 4839
(2007/10/03)
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- Catalytic amination reactions mediated by Co(II) Schiff base complexes
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Co(acacen), 1, (acacen = 2,11-dihydroxy-4,9-dimethyl-5,8-diaza-2,4,8,10- dodecatetraene dianion) was found to be a highly efficient catalyst for the allylic amination of non activated alkenes, using N-(p-toluensulfonyl) iminophenyliodinane (PhINTs) as nitrene precursor. This reactivity has been extended to the less reactive C-H bond of toluene. The effect of reaction times and of added cosolvent on yields and selectivities was investigated. Under the best conditions, allylic amines were obtained in a 40-70% isolated yield. A complex derived from the stoichiometric reaction of Co(acacen), 1, with PhINTs has been isolated and spectroscopically characterized. Such a complex, although not able to transfer its NTs moiety to alkenes, is still active in catalyzing allylic amination of cyclohexene.
- Caselli, Alessandro,Gallo, Emma,Ragaini, Fabio,Oppezzo, Alessandro,Cenini, Sergio
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p. 2142 - 2148
(2007/10/03)
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- Lewis base catalyzed ring opening of aziridines with silylated nucleophiles
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(Chemical Equation Presented) The ring opening of N-tosylaziridines with trimethylsilylated nucleophiles, catalyzed by N,N,N′,N′- tetramethylethylenediamine, led to the production of β-functionalized sulfonamides in good to excellent yields with high regi
- Minakata, Satoshi,Okada, Yuriko,Oderaotoshi, Yoji,Komatsu, Mitsuo
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p. 3509 - 3512
(2007/10/03)
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- Facile alkane functionalization in copper-[2.1.1]-(2,6)-pyridinophane- PhINTs systems
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Mild catalytic dehydrogenation of cycloalkanes (cyclo-C5H 10, cyclo-C6H12, cyclo-C8H 16) and aziridination of resulting olefins is reported with PhINTs and copper-[2.1.1]-(2,6)-pyridinophane (L) complexes LCuXn (n = 1, 2; X = Cl, OTf) "activated" with NaBArF4 in dichloromethane solution.
- Vedernikov, Andrei N.,Caulton, Kenneth G.
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p. 162 - 163
(2007/10/03)
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- Silica-Water Reaction Media: Its Application to the Formation and Ring Opening of Aziridines
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Olefins can be converted into aziridines by using a chloramine-T/I 2 system, and silica and water as the reaction medium (see picture). Moreover, the ring-opening reaction of the resulting aziridine with an azide or a cyanide ion proceeds in th
- Minakata, Satoshi,Kano, Daisuke,Oderaotoshi, Yoji,Komatsu, Mitsuo
-
-
- Angular ligand constraint yields an improved olefin aziridination catalyst
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(Matrix presented) The use of a pyridinophane, a macrocycle composed of three pyridines linked, via all ortho positions through CH2 or CH2CH2 groups, bound to copper, gives good performance (rate and yield) catalyzing the
- Vedernikov, Andrei N.,Caulton, Kenneth G.
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p. 2591 - 2594
(2007/10/03)
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- On the α-lithiation-rearrangement of N-toluensulfonyl aziridines: Mechanistic and synthetic aspects
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A detailed study of the rearrangement of five cycloalkene N-toluenesulfonyl (tosyl) aziridines using sec-butyllithium (with and without added ligands such as (-)-sparteine and TMEDA) has been carried out. Allylic sulfonamides were the main products from the cyclopentene and cyclohexene aziridines whereas bicyclic sulfonamides were obtained from the cycloheptene and cyclooctene aziridines. In most cases, p-toluenesulfonamide (TsNH 2) was produced as a by-product and a mechanistic explanation for its formation is forwarded. These reactions are believed to involve α-lithiation to a lithiated aziridine which can then partition through two pathways: (i) rearrangement to allylic or bicyclic sulfonamides via C-H insertion reactions or (ii) reductive alkylation to alkenes via attack by sec-butyllithium and subsequent elimination of TsNH2. In the (-)-sparteine reactions, the products were generated with 38-66% ee and the sense of asymmetric induction involved lithiation of the S-aziridine stereocentre. This is opposite to that observed with epoxides.
- O'Brien, Peter,Rosser, Clare M.,Caine, Darren
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p. 9779 - 9791
(2007/10/03)
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- Efficient ring opening reactions of N-tosyl aziridines with amines and water in presence of catalytic amount of cerium(IV) ammonium nitrate
-
While methyl- and benzylamines opened N-tosyl aziridines 1 very efficiently in acetonitrile with complete regio- and stereoselectivity to give the corresponding diamines 2 and 3, respectively, in excellent yields, similar openings with water could only be achieved in the presence of a catalytic amount of cerium(IV) ammonium nitrate under very mild conditions furnishing the amino alcohols 4.
- Chakraborty, Tushar K.,Ghosh, Animesh,Raju, T. Venugopal
-
-
- Synthesis of novel sila-substituted β-amino acids
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A highly efficient and stereoselective synthesis of unnatural cyclic sila-substituted β-amino acids has been developed from simple starting materials. The key step is nucleophilic ring opening of an intermediate aziridine with an umpolung synthon for the
- Matthews, Jennifer L,McArthur, Duncan R,Muir, Kenneth W
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p. 5401 - 5404
(2007/10/03)
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- Base-promoted elaboration of aziridines
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The base-promoted isomerization of aziridines to allyl amines is still an almost unknown reaction. However, the use of superbasic reagents has shown to be able to promote a regio- and stereoselective conversion of monocyclic and bicyclic sulfonyl aziridin
- Mordini, Alessandro,Russo, Francesco,Valacchi, Michela,Zani, Lorenzo,Degl'Innocenti, Alessandro,Reginato, Gianna
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p. 7153 - 7163
(2007/10/03)
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