149552-43-2Relevant articles and documents
Expedient Synthesis of 2-Iminothiazolidines via Telescoping Reactions Including Iron-Catalyzed Nitrene Transfer and Domino Ring-Opening Cyclization (DROC)
Coin, Guillaume,de Ferrier de Montal, Oriane,Dubourdeaux, Patrick,Latour, Jean-Marc
, p. 443 - 448 (2021)
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
On the enantioselectivity of aziridination of styrene catalysed by copper triflate and copper-exchanged zeolite Y: Consequences of the phase behaviour of enantiomeric mixtures of N-arene-sulfonyl-2-phenylaziridines
Jeffs, Laura,Arquier, Damien,Kariuki, Benson,Bethell, Donald,Page, Philip C. Bulman,Hutchings, Graham J.
, p. 1079 - 1084 (2011)
By synthesising S-2-phenyl-N-(4-nitrophenyl)aziridine from S-phenylglycinol, it has been demonstrated that the aziridination of styrene by [N-(4-nitrobenzenesulfonyl)imino]phenyliodinane (nosyliminophenyliodinane, PhINNs) in the presence of S,S-2,2′-isopr
Catalytic asymmetric heterogeneous aziridination of styrene using Cu 2+ -exchanged zeolite Y: Effect of the counter-cation on enantioselectivity and on the reaction profile
Gullick, John,Ryan, Darragh,McMorn, Paul,Bethell, Donald,King, Frank,Hancock, Frederick,Hutchings, Graham
, p. 1470 - 1478 (2004)
Effective catalysts have Cu2+ -exchange levels of ca. 40-60% of the maximum concentration for electroneutrality and, consequently, Cu-zeolite Y catalysts contain an additional counter-cation (H+, Li-, Na+, Ksup
CO2-activated NaClO-5H2O enabled smooth oxygen transfer to iodoarene: A highly practical synthesis of iodosylarene
Miyamoto, Kazunori,Watanabe, Yuichiro,Takagi, Taisei,Okada, Tomohide,Toyama, Takashi,Imamura, Shinji,Uchiyama, Masanobu
, (2021/05/27)
A safe, rapid, and environmentally friendly synthesis of iodosylarene (ArIO) has been developed using NaClO under a carbon dioxide (CO2) atmosphere. Exposure of iodoarene to NaClO-5H2O in acetonitrile under CO2 (1 atm) resulted in the clean formation of ArIO within 10 minutes in high yield. The absence of a base in this method enables the direct use of in-situ-generated iodosylarene not only for a variety of oxidative transformations (synthesis of sulfilimine, pentavalent bismuth, benzyne adduct, etc.), but also for the synthesis of iodonium ylide and imino-λ3-iodane in one pot.
Ligand Redox Noninnocence in [CoIII(TAML)]0/- Complexes Affects Nitrene Formation
De Bruin, Bas,Oudsen, Jean-Pierre H.,Rietdijk, Niels R.,Siegler, Maxime A.,Tepaske, Martijn A.,Tromp, Moniek,Van Der Vlugt, Jarl Ivar,Van Leest, Nicolaas P.,Venderbosch, Bas
supporting information, p. 552 - 563 (2020/02/20)
The redox noninnocence of the TAML scaffold in cobalt-TAML (tetra-amido macrocyclic ligand) complexes has been under debate since 2006. In this work, we demonstrate with a variety of spectroscopic measurements that the TAML backbone in the anionic complex [CoIII(TAMLred)]- is truly redox noninnocent and that one-electron oxidation affords [CoIII(TAMLsq)]. Multireference (CASSCF) calculations show that the electronic structure of [CoIII(TAMLsq)] is best described as an intermediate spin (S = 1) cobalt(III) center that is antiferromagnetically coupled to a ligand-centered radical, affording an overall doublet (S = 1/2) ground-state. Reaction of the cobalt(III)-TAML complexes with PhINNs as a nitrene precursor leads to TAML-centered oxidation and produces nitrene radical complexes without oxidation of the metal ion. The ligand redox state (TAMLred or TAMLsq) determines whether mono-or bis-nitrene radical complexes are formed. Reaction of [CoIII(TAMLsq)] or [CoIII(TAMLred)]- with PhINNs results in the formation of [CoIII(TAMLq)(Na￠Ns)] and [CoIII(TAMLq)(Na￠Ns)2]-, respectively. Herein, ligand-to-substrate single-electron transfer results in one-electron-reduced Fischer-type nitrene radicals (Na￠Ns-) that are intermediates in catalytic nitrene transfer to styrene. These nitrene radical species were characterized by EPR, XANES, and UV-vis spectroscopy, high-resolution mass spectrometry, magnetic moment measurements, and supporting CASSCF calculations.
Uncatalyzed Oxidative C?H Amination of 9,10-Dihydro-9-Heteroanthracenes: A Mechanistic Study
van Leest, Nicolaas P.,Grooten, Lars,van der Vlugt, Jarl Ivar,de Bruin, Bas
supporting information, p. 5987 - 5993 (2019/04/03)
A new method for the one-step C?H amination of xanthene and thioxanthene with sulfonamides is reported, without the need for any metal catalyst. A benzoquinone was employed as a hydride (or two-electron and one-proton) acceptor. Moreover, a previously unknown and uncatalyzed reaction between iminoiodanes and xanthene, thioxanthene and dihydroacridines (9,10-dihydro-9-heteroanthracenes or dihydroheteroanthracenes) is disclosed. The reactions proceed through hydride transfer from the heteroarene substrate to the iminoiodane or benzoquinone, followed by conjugate addition of the sulfonamide to the oxidized heteroaromatic compounds. These findings may have important mechanistic implications for metal-catalyzed C?H amination processes involving nitrene transfer from iminoiodanes to dihydroheteroanthracenes. Due to the weak C?H bond, xanthene is an often-employed substrate in mechanistic studies of C?H amination reactions, which are generally proposed to proceed via metal-catalyzed nitrene insertion, especially for reactions involving nitrene or imido complexes that are less reactive (i.e., less strongly oxidizing). However, these substrates clearly undergo non-catalyzed (proton-coupled) redox coupling with amines, thus providing alternative pathways to the widely assumed metal-catalyzed pathways.
Double Functionalization of Styrenes by Cu-Mediated Assisted Tandem Catalysis
Kawauchi, Daichi,Ueda, Hirofumi,Tokuyama, Hidetoshi
supporting information, p. 2056 - 2060 (2019/03/13)
The double functionalization of styrenes through Cu-mediated assisted tandem catalysis was developed. The reaction was initiated by Cu-catalyzed aziridination and the subsequent nucleophilic ring-opening, which was triggered by the addition of (NH4)2S2O8 as an oxidant of Cu-catalyst to form a variety of C–C and C–X bonds. The expansion to three contiguous catalytic cycles led to the synthesis of functionalized indolines by one-pot operation.
Design, synthesis, and antiplasmodial evaluation of a series of novel sulfoximine analogues of carbohydrate-based thiochromans
Chizema, Munashe,Mabasa, Tommy F.,Hoppe, Heinrich C.,Kinfe, Henok H.
, p. 254 - 261 (2018/11/23)
Sulfone/sulfoxide-containing carbohydrate derived thiochromans were found to be highly active antiplasmodial agents. However, the inability of the sulfone/sulfoxide functional groups for further derivatization and manipulation limited the potential for further exploration. In this study, based on the interesting and important physicochemical properties, as well as amenability of sulfoximines (isosters of sulfones) for further derivatization, a series of novel sulfoximine-type carbohydrate-derived thiochroman derivatives have been successfully synthesized, characterized, and evaluated for their antiplasmodial activity. Although the replacement of the sulfone functional group with a sulfoximine unit improved the antiplasmodial activity of the scaffolds, the activity was highly dependent on the configuration of the stereogenic centre at the sulfur atom. Moreover, analysis of the crystal structures of the sulfoximine analogues revealed that the bond between the sulfur and nitrogen atoms of the sulfoximine functional group is not a true double bond but rather a polarized single bond.
Iron(MCP) Complexes Catalyze Aziridination with Olefins As Limiting Reagents
Shehata, Mina F.,Ayer, Suraj K.,Roizen, Jennifer L.
, p. 5072 - 5081 (2018/05/15)
Herein described are the first efficient nitrogen-atom transfer reactions mediated by iron N,N′-dimethyl-N,N′-bis(2-pyridinylmethyl)cyclohexane-1,2-diamine- (MCP-) and 2-({1-[(pyridin-2-ylmethyl)pyrrolidin-2-yl]pyrrolidin-1-yl}methyl)pyridine-type (PDP-type) complexes. These catalysts affect styrene aziridination under mild conditions based on a limiting quantity of olefin substrate.
Safer Synthesis of (Diacetoxyiodo)arenes Using Sodium Hypochlorite Pentahydrate
Watanabe, Ayumi,Miyamoto, Kazunori,Okada, Tomohide,Asawa, Tomotake,Uchiyama, Masanobu
, p. 14262 - 14268 (2018/11/23)
A practical method for the preparation of (diacetoxyiodo)arene ArI(OAc)2 is described. The use of commercially available sodium hypochlorite pentahydrate (NaClO·5H2O) enabled safe, rapid, and inexpensive oxidation of iodoarenes with electron-withdrawing and -donating substituents. The method allows tandem divergent access to synthetically useful organo-λ3-iodanes such as hydroxyl(tosyloxy)iodobenzene, iodosylbenzene, iodonium ylide, etc.
