- Visible-Light-Promoted Polysubstituted Olefins Synthesis Involving Sulfur Ylides as Carbene Trapping Reagents
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A blue-light-emitting diode (LED) promoted coupling of aryl diazoacetates with sulfur ylides is described. This protocol features mild conditions, good functional group tolerance, and broad substrate scope for both aryl diazoacetates with sulfur ylides. Under optimal reaction conditions, a wide range of trisubstituted olefins is obtained in moderate to good yield, which can be further transferred to other biologically important heterocycles after a two-step simple operation.
- Ye, Cong,Cai, Bao-Gui,Lu, Juan,Cheng, Xiao,Li, Lei,Pan, Zhong-Wen,Xuan, Jun
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p. 1012 - 1022
(2021/01/09)
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- Photo/N-Heterocyclic Carbene Co-catalyzed Ring Opening and γ-Alkylation of Cyclopropane Enal
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An unprecedented photo/NHC-co-catalyzed ring-opening C-C bond cleavage of cyclopropane enal and the following γ-alkylation with a halogenated compound via radicals were established, affording the corresponding γ-alkylated α,β-unsaturated esters in moderate to good yields.
- Dai, Lei,Ye, Song
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p. 986 - 990
(2020/02/28)
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- Synthesis of functionalized thietanes via electrophilic carbenoid-induced ring expansion of thiiranes with sulfonium acylmethylides as carbene precursors
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Various functionalized thietanes were prepared from thiiranes via an electrophilic ring expansion with rhodium carbenoids as electrophiles generated from safe and readily accessible dimethylsulfonium acylmethylides. The reaction appears to proceed through electrophilic metallocarbenoid-induced activation of thiiranes, nucleophilic ring-opening of the activated thiiranes with dimethyl sulfide as a transient nucleophile, and nucleophilically intramolecular cyclization. The Umpolung from the nucleophilic ylides to the electrophilic carbenoids plays an important role in both the activation and ring opening of thiiranes and subsequent cyclization. The current method provides a new strategy for the efficient preparation of functionalized thietanes from readily available thiiranes.
- Dong, Jun,Du, Hongguang,Xu, Jiaxi
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p. 10724 - 10739
(2019/09/30)
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- Ring-opening cyclization of spirocyclopropanes with stabilized sulfonium ylides for the construction of a chromane skeleton
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Regioselective ring-opening cyclization of cyclohexane-1,3-dione-2-spirocyclopropanes with stabilized sulfonium ylides provided 2,3-trans-disubstituted 2,3,4,6,7,8-hexahydro-5H-1-benzopyran-5-ones in high yields without the formation of any isomers. The o
- Nambu, Hisanori,Onuki, Yuta,Ono, Naoki,Tsuge, Kiyoshi,Yakura, Takayuki
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supporting information
p. 6539 - 6542
(2019/06/13)
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- New Pd(II) complexes of sulfur ylides; Synthesis, X-ray characterization, a theoretical study and catalytic activity toward the Mizoroki-Heck reaction
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The reaction of sulfur ylides (L) SMe2C(H)C(O)R (R = 4-nitrophenyl, phenyl, and 3-nitrophenyl) with the dichloro(1,5-cyclooctadiene)palladium(II) complex, [PdCl2(cod)], in a 2:1 ratio gives the new Pd(II) complexes of type cis- and trans-[PdCl2(SMe2C(H)C(O)R)2] (R = phenyl (1), 3-nitrophenyl (2), and 4-nitrophenyl (3)). Characterization of the obtained complexes was performed by elemental analysis, IR, 1H, 13C NMR and mass spectroscopies. Also, the structure of complex trans-[PdCl2(SMe2C(H)C(O)C6H4-p-NO2)2] (3) was characterized by single crystal X-ray analysis. The X-ray crystallography results reveal that the structure of complex 3 contains two Cα-coordinated sulfur ylide ligands in trans geometry. These air/moisture stable complexes were also employed as efficient catalysts for the Mizoroki-Heck cross-coupling reaction of several aryl halides with olefins. The coupled products of these reactions were obtained in good to excellent yields and purity, short reaction times and low catalyst loading. Also a theoretical study on the structure of the complexes 1-3 have been investigated at the BP86/def2-SVP level of theory. The bonding situation between the [PdCl2] and L2 fragments [(Ylide)2] in the [L2PdCL2] complexes, were carried out by NBO and energy-decomposition analysis (EDA), as well as their natural orbitals for chemical valence variation (EDA-NOCV). The results confirmed that the contribution of the electrostatic interactions in the Pd-C bond in the complexes is about 50%.
- Sabounchei,Ahmadianpoor,Yousefi,Hashemi,Bayat,Sedghi,Akhlaghi Bagherjeri,Gable
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p. 28308 - 28315
(2016/04/09)
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- Functionalized α-keto stabilized sulfonium ylides as highly active ligand precursors for palladium catalyzed Suzuki-Miyaura cross-couplings
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Five α-keto stabilized sulfonium ylides as type (Me) 2SCHC(O)C6H4-p-X (X = H, Br, NO2, CH3 and OCH3) {L1-L5} were used as ligand precursors in the Suzuki-Miyaura cross-coupling reaction. The best catalytic performance was obtained by using a sulfonium ylide/Pd ratio of 2:1. The catalytic systems displayed high activities, which increased in the order R = NO2 (L3) 2) 1) 3 (L4) 3 (L5). The coupling reactions proceeded smoothly with 0.05 mol% PdCl2 and 0.1 mol% L5 in DMF at 130 °C between varieties of electronically activated, deactivated and neutral aryl halides and aryl boronic acids within short reaction times and without the need for exclusion of air which gave good to high yields of the corresponding products. All the studied ligands demonstrated very high activity in the Suzuki-Miyaura cross-coupling, which yielded turnover numbers up to 1940. Comparative studies showed that the performance of sulfonium ylide L5 is significantly superior to that of related phosphine-free ligands.
- Sabounchei, Seyyed Javad,Hashemi, Ali
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p. 123 - 127
(2014/08/18)
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- Reactivity of mercury(II) halides with the α-keto stabilized sulfonium ylides: Crystal structures of two new polymer and binuclear complexes and in vitro antibacterial study
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Reaction of α-keto stabilized sulfonium ylides (Me) 2SCHC(O)C6H4R (R = p-NO2 (Y) and p-Br(Y′)) with HgX2 (X = Cl, Br and I) in equimolar ratios using methanol as solvent leads to two types of products. Single crystal X-ray diffraction analysis reveals (i) binuclear complex of [HgI2(Y)] 2 (3) with an asymmetric halide-bridged structure and (ii) one-dimensional polymer of [HgI2(Y′)]n (6) that the monomeric -Hg-I-Hg- bridging leads to a zig-zag polymeric chain in which mercury assumes a distorted tetrahedral geometry. Characterization of the compounds by IR, 1H and 13C NMR spectroscopy confirmed coordination of the ylide to the metal through the carbon atom. Analytical data indicate a 1:1 stoichiometry between the ylide and Hg(II) halide in all of products. The Hg(II) complexes with different ligands evaluated for their antibacterial activity using disc diffusion method. The results show that all complexes represent antibacterial activity against bacteria tested especially on Gram positive ones.
- Sabounchei, Seyyed Javad,Bagherjeri, Fateme Akhlaghi,Boskovic, Colette,Gable, Robert W.,Karamian, Roya,Asadbegy, Mostafa
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- Synthesis and characterization of novel simultaneous C and O-coordinated and nitrate-bridged complexes of silver(i) with carbonyl-stabilized sulfonium ylides and their antibacterial activities
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Reaction of sulfonium ylides (Me)2SCHC(O)C6H 4R (R = H; m-NO2; p-NO2; p-OMe; p-Me and p-Br) with AgNO3 in dichloromethane leads to various compounds. Single crystal X-ray diffraction analysis reveals that the adducts take 3 forms: (i) two-dimensional polymer, [AgNO3(Me2SCHC(O)C 6H5)]n (1), with nitrate bridges in which each nitrate coordinates to three silver atoms through two oxygen atoms and two Me2SCHC(O)C6H5 ligands coordinate to silver centers through carbon atoms; (ii) cationic binuclear, [Ag(Me 2SCHC(O)C6H4-m-NO2) 2]2(NO3)2·2H2O (2), in which Me2SCHC(O)C6H4-m-NO2 ligands simultaneously coordinate through both carbon and oxygen atoms with nitrate as a counter ion, and (iii) cationic mononuclear and anionic binuclear, [Ag(Me2SCHC(O)C6H4-p-NO2) 2]2[{AgNO3(μ-NO3) (Me 2SCHC(O)C6H4-p-NO2)} 2]·2CH3OH (3), in which nitrate groups act as bridging as well as terminal ligands, and Me2SCHC(O)C 6H4-p-NO2 ligands display C-coordination. Characterization of the obtained compounds was also performed by infrared, 1H- and 13C-NMR spectroscopy and analytical data indicated a 1:2 stoichiometry between the silver(i) nitrate and ylide p-OMe (4) and 1:1 for ylides p-Me (5) and p-Br (6). In addition, the antibacterial effects of DMSO-solutions of complexes 1-6 were evaluated by the agar disc diffusion method against three Gram positive and three Gram negative bacteria. All complexes displayed antibacterial activity against these bacteria, with high levels of inhibitory potency exhibited against the Gram negative species.
- Sabounchei, Seyyed Javad,Akhlaghi Bagherjeri, Fateme,Mozafari, Zeinab,Boskovic, Colette,Gable, Robert W.,Karamian, Roya,Asadbegy, Mostafa
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p. 2520 - 2529
(2013/04/10)
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- Unusual fluorescent properties of novel fluorophores, 6-aryl-3,4-diphenyl-α-pyrone derivatives
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Novel fluorophores, 6-aryl-3,4-diphenyl-α-pyrones, were synthesized and their spectroscopic properties investigated in the form of evaporated films on plain glass slides, as well as in the solid and solution states. An electron-donating aryl group on the 6-position of the pyrones causes a red-shift in the absorption and fluorescent maxima. In the solid states, they show intense blue-to-orange fluorescence, but not in solution. This unusual fluorescent property is caused by fixing the 6-aryl group of the pyrones, and is the result of molecular packing. These interactions induce a pathway for radiative decay, which is associated with intense fluorescence emission only in the solid state.
- Hirano,Minakata,Komatsu
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p. 1567 - 1575
(2007/10/03)
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