175222-83-0Relevant academic research and scientific papers
Wheel-to-rhomboid isomerization as well as nitrene transfer catalysis of ruthenium-thiolate wheels
Tso, Ken Chi-Hang,Chan, Sharon Lai-Fung,Huang, Jie-Sheng,Che, Chi-Ming
, p. 2419 - 2422 (2017)
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/
A method for rhodium(II)-catalyzed aziridination of olefins
Mueller, Paul,Baud, Corine,Jacquier, Yvan
, p. 1543 - 1548 (1996)
The [Rh2(OAc)4] catalyzed decomposition of (N-(p-nitrobenzenesulfonyl)imino)phenyliodinane (PhI=NNs) in the presence of olefins affords aziridines in yields of 18-85%. The aziridination of cis-β-methylstyrene (1h) and cis-hex-2-ene (
Studies on the formal [3 + 2] cycloaddition of aziridines with alkenes for the synthesis of 1-azaspiroalkanes
Martinand-Lurin, Elodie,Gruber, Raymond,Retailleau, Pascal,Fleurat-Lessard, Paul,Dauban, Philippe
, p. 1414 - 1426 (2015)
The Lewis acid-mediated [3 + 2] cycloaddition of N-sulfonyl- and N-sulfamoylaziridines with alkenes provides a rapid and efficient access to 1-azaspiro[4.n]alkanes. Experimental studies have been combined with DFT calculations to explore the mechanism of the reaction. They demonstrate that the nature of the electron-withdrawing nitrogen protecting group has a very limited influence on the course of the reaction and, particularly, on the initial formation of the 1,3-zwitterionic species through C-N bond cleavage, which has been found to be the rate-determining step. Compared to N-sulfonylaziridines, N-sulfamoylaziridines have proved to be more synthetically useful synthons that afford crystalline polycyclic structures in good yields. A short sequence of catalytic C(sp3)-H amination-cyclization-[3 + 2] cycloaddition has then been successfully designed to afford the homologue 1-azaspiro[5.n]alkanes, thereby illustrating the higher versatility of sulfamates in these cycloadditions.
Catalytic Chemoselective Sulfimidation with an Electrophilic [CoIII(TAML)]?-Nitrene Radical Complex**
van Leest, Nicolaas P.,van der Vlugt, Jarl Ivar,de Bruin, Bas
, p. 371 - 378 (2020/12/01)
The cobalt species PPh4[CoIII(TAMLred)] is a competent and stable catalyst for the sulfimidation of (aryl)(alkyl)-substituted sulfides with iminoiodinanes, reaching turnover numbers up to 900 and turnover frequencies of 640 min?1 under mild and aerobic conditions. The sulfimidation proceeds in a highly chemoselective manner, even in the presence of alkenes or weak C?H bonds, as supported by inter- and intramolecular competition experiments. Functionalization of the sulfide substituent with various electron-donating and electron-withdrawing arenes and several alkyl, benzyl and vinyl fragments is tolerated, with up to quantitative product yields. Sulfimidation of phenyl allyl sulfide led to [2,3]-sigmatropic rearrangement of the initially formed sulfimide species to afford the corresponding N-allyl-S-phenyl-thiohydroxylamines as attractive products. Mechanistic studies suggest that the actual nitrene transfer to the sulfide proceeds via (previously characterized) electrophilic nitrene radical intermediates that afford the sulfimide products via electronically asynchronous transition states, in which SET from the sulfide to the nitrene radical complex precedes N?S bond formation in a single concerted process.
Transition-Metal-Free Stereospecific Oxidative Annulative Coupling of Indolines with Aziridines
Karjee, Pallab,Sarkar, Tanumay,Kar, Subhradeep,Punniyamurthy, Tharmalingam
, p. 8261 - 8270 (2020/07/25)
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.
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.
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.
Rhodium(III)-catalyzed Intermolecular Unactivated Secondary C(sp3)?H Bond Amidation Directed by 3,5-dimethylpyrazole
Wang, Yanwei,Liu, Hongxin,Li, Bin,Wang, Baiquan
supporting information, p. 1564 - 1569 (2019/02/19)
A Rh(III)-catalyzed intermolecular unactivated secondary C(sp3)?H bond amidation via nitrene insertion directed by 3,5-dimethylpyrazole is reported. This procedure tolerates a broad substrate scope including chain and cyclic N-alklyamides. Notably, the directing group 3,5-dimethylpyrazole of chain N-alkylamide substrates could be easily removed via cascade intermolecular amidation and intramolecular cyclization in one-pot affording the sulfonylureas by increasing the reaction temperature. (Figure presented.).
Cycloaddition of α-Diazocarbonyl Compounds and N-Tosylaziridines: Synthesis of Polysubstituted 2 H-1,4-Oxazines through Synergetic Catalysis of AgOTf/Cu(OAc)2
Fang, Shangwen,Zhao, Yanwei,Li, Haiyan,Zheng, Yonggao,Lian, Pengcheng,Wan, Xiaobing
supporting information, p. 2356 - 2359 (2019/03/29)
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.
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.
