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1.
《Tetrahedron: Asymmetry》1999,10(16):3095-3098
The use of sterically congested C2-symmetrical bis(oxazoline) ligands with methylene and ethylene spacers between the oxazoline rings results in the reversal of the enantioselection for aldol reactions catalyzed by bis(oxazoline)–Cu(II) complexes. 相似文献
2.
Enantioselective recognition of amino acids has been studied with C2-symmetric chiral pyridine bis(oxazoline)-copper(II) complexes at physiological pH condition. UV-visible titration revealed strong binding of submillimolar dissociation constant between pyridine bis(oxazoline)-copper(II) complex and amino acids in aqueous solution. Moderate selectivity of up to 2:1 between d- and l-amino acids was achieved. The enantiomers were baseline resolved by capillary electrophoresis, using the bis(l-lysine)-copper(II) complex as a chiral selector. 相似文献
3.
ME Owen E Carter GJ Hutchings BD Ward DM Murphy 《Dalton transactions (Cambridge, England : 2003)》2012,41(36):11085-11092
X- and Q-band EPR and ENDOR spectroscopy was used to study the structure of a series of heteroleptic and homoleptic copper bis(oxazoline) complexes, based on the (-)-2,2'-isopropylidenebis[(4S)-4-phenyl-2-oxazoline] ligand and bearing different counterions (chloride versus triflate); labelled [Cu(II)()]. The geometry of the two heteroleptic complexes, [Cu(II)()] and [Cu(II)()], depended on the choice of counterion. Formation of the homoleptic complex was only evident when the Cu(II)(OTf)(2) salt was used (Cu(II)(Cl)(2) inhibited the transformation from heteroleptic to homoleptic complexes). The hyperfine and quadrupole parameters for the surrounding ligand nuclei were determined by ENDOR. Well resolved (19)F and (1)H couplings confirmed the presence of both coordinated water and TfO(-) counterions in [Cu()]. 相似文献
4.
Thorhauge J Roberson M Hazell RG Jørgensen KA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(8):1888-1898
The intermediates in the chiral bis(oxazoline)copper(II)-catalyzed reactions have been investigated by means of experimental and theoretical investigations. It is shown that the absolute configuration of the hetero-Diels-Alder adduct obtained from the reaction of ethyl glyoxylate with 1,3-cyclohexadiene in the presence of the chiral bis(phenyloxazoline)copper(II) is dependent on the solvent. In this case, a linear relationship between the enantiomeric excess (ee) and the dielectric constant of the solvent was observed. However, the enantiomeric excess for the adduct obtained with the chiral bis(tert-butyloxazoline)copper(II) complex is independent of the solvent. The addition of different coordinating solvents to the chiral catalysts was investigated and no effect on the enantioselectivity of the reaction was observed. A series of chiral bis(tert-butyloxazoline)-, bis(phenyloxazoline)-, and bis(indaneoxazoline)copper(II) complexes has been prepared and characterized by X-ray analysis, and the similarity between the structures is discussed. For comparison, two related chiral bis(tert-butyloxazoline)- and bis(phenyloxazoline)zinc(II) complexes were also prepared and characterized. A series of chiral bis(oxazoline)copper(II)-substrate (the substrate being glyoxal or methyl glyoxylate) complexes was investigated by means of ab initio calculations. Calculation of the total energy of the optimized structure of 17-, 19-, and 21-electron bis(oxazoline)copper(II)-substrate complexes give the 17-electron complex as the most stable and the most reactive complex, while the 21-electron complex is less stable and also much less reactive. The optimized structures of both the 17-electron bis(tert-butyloxazoline)- and bis(phenyloxazoline)copper(II)-substrate complexes show that the plane of the substrate molecule is twisted by approximately 40-45 degrees out of the bis(oxazoline)copper(II) plane, in agreement with the X-ray structures. On the basis of the experimental results, X-ray structures, and ab initio calculations, the structure of the intermediate(s) and reactivity of the chiral bis(oxazoline)copper(II)-substrate complexes are discussed. 相似文献
5.
《Tetrahedron: Asymmetry》2001,12(21):2937-2939
Hetero Diels–Alder reactions of 1,3-cyclohexadiene with N-sulfinyl dienophiles 1a or 1b, promoted by Cu(II)- or Zn(II)-chiral bis(oxazoline) complexes, afforded endo adducts in high yields (up to 85%) and enantiomeric excess (e.e. of up to >98%) under stoichiometric conditions. With 10 mol% loading of the Zn(II) catalyst up to 75% e.e. was obtained for the endo adduct (endo:exo=10:1, total yield 68%). 相似文献
6.
Vesna ?aplar Zlata Raza Vladislav Tomiši? Josip Po?ar Mladen ?ini? 《Tetrahedron》2004,60(37):8079-8087
Silver(I) and copper(I) complexes of C2-symmetric bis(oxazoline) ligands were studied by UV, NMR, IR, EPR and ES-MS spectroscopies. The stability constants of the Ag-1a and Ag-1b complexes with 1:1 and 1:2 stoichiometries in acetonitrile were determined by NMR spectrometric titrations. The evidence of tetrahedral coordination for complex (Ag(1a)2(+ was obtained from the complexation induced shifts (CIS) and NOEs. Mass spectra revealed the Cu(II) mediated oxidation of methylene bridge in copper complexes of 1a and 1b, which was in accordance with the UV, NMR, IR and EPR findings. The efficiency of Cu(I) complexes of methylene-bridged 1,5-bis(oxazoline)s 1 as chiral catalysts in stereoselective cyclopropanation of styrene with ethyl diazoacetate, was compared to that of the dialkylmethylene-bridged 1,5-bis(oxazoline)s 2. 相似文献
7.
[reaction: see text] C(2)-symmetric tridentate bis(oxazoline) and bis(thiazoline) ligands with a diphenylamine backbone have been investigated in the catalytic asymmetric Henry reaction of alpha-keto esters with different Lewis acids. Their Cu(OTf)(2) complexes furnished S enantiomers, while Et(2)Zn complexes afforded R enantiomers, both of them with higher enantioselectivities (up to 85% ee). Reversal of enantioselectivity in asymmetric Henry reactions was achieved with the same chiral ligand by changing the Lewis acid center from Cu(II) to Zn(II). The results show that the NH group in C(2)-symmetric tridentate chiral ligands plays a very important role in controlling both the yields and enantiofacial selectivity of the Henry products. 相似文献
8.
For evaluation of a chiral C2-symmetric bis(oxazoline) ligand, its Lewis acid complexes-catalyzed asymmetric 1,3-dipolar cycloaddition reactions of nitrones with electron-deficient dipolarophiles, 3-(2-alkenoyl)-1,3-oxazolidin-2-ones, have been investigated and it was found that the cycloadditions using a Cu(II)-bis(oxazoline) complex under optimized reaction conditions induced extremely high enantioselectivity. 相似文献
9.
New bis(oxazoline) ligands (BOXs) containing biaryl substitutents at the C-4 position and H or CH2OR substituents at the C-5 position have been synthesized using Suzuki cross-coupling as the main tool for structural diversity. Copper, zinc, and palladium complexes of the prepared BOXs have been evaluated in the following catalytic asymmetric processes: Acylation with kinetic resolution of trans-1,2-cyclohexanediol (Cu), enantioselective Friedel-Crafts alkylation of indole (Zn), and enantioselective alkylation of 3-acetoxy-1,3-diphenylpropene (Pd). 相似文献
10.
11.
《Tetrahedron》2003,59(39):7751-7760
Macrocyclic bis(α-amino acids) cis- and trans-2a-b were prepared from the selectively protected tris(hydroxymethyl)aminomethane 3. The X-ray structures of the free bis(amino acids) and/or of the corresponding Cu(II) complexes have been determined allowing an unambiguous configurational assessment. At the same time, conformational in-out dichotomy of the functional groups has been demonstrated in the bis(amino acids) as well as in their Cu(II) complexes. 相似文献
12.
Patrick O'Leary Krijn P. De Jong Robertus J.M. Klein Gebbink 《Tetrahedron letters》2004,45(16):3177-3180
Two chiral copper(II) bis(oxazoline) complexes have been immobilized on silica via electrostatic interactions using a remarkably straightforward procedure. The immobilized catalysts were tested in a standard Diels-Alder reaction and gave surprising results. Where the immobilized Cu((S,S)-phenyl-box)(OTf)2 catalyst was used, the predominant enantiomer formed was the opposite of that produced using the same catalyst in a homogeneous reaction. This is a startling result given that the only difference is the electrostatic immobilization of the catalyst on amorphous silica. The activity of the catalyst in a hetero Diels-Alder reaction was also tested. This catalyst was also recycled, successfully maintaining a similar activity to the homogeneous analogue through a number of cycles. 相似文献
13.
In recent years, C2-symmetric chiral bis (oxazoline) ligand-metal complexes have received a great of attention through their use in various catalytic processes[1-2]. Since the early 1990s, many impressive enantioselective carbon-carbon bond forming reactions, aziridination reactions, hydrosilylations, oxidations and reductions have been recorded using bis (oxazoline)-metal complexes with wide structural diversity[3-4]. The latest review is intended to focus on the recent developments of bis(oxazoline) ligand-metal catalyzed asymmetric reactions and their applications in organic synthesis. Herein we intend to report the synthesis of a new type of chiral bis(oxazoline), 1,3-bis(oxazolinyl)benzene. Application of their asymmetric catalysis is under working. 相似文献
14.
A series of chiral C2-symmetric bis(oxazoline) ligands containing dibenzo[a,c]cycloheptadiene units were synthesized. The copper complexes, prepared in situ from copper (I)-triflate and the new enantiopure oxazoline ligands, were assessed as chiral catalysts in the enantioselective cyclopropanation of styrene with diazoacetate. Enantioselectivities up to 82 and 62%, respectively, for trans- and cis-2-phenylcyclopropanecarboxylate were observed. 相似文献
15.
《Tetrahedron letters》2014,55(50):6803-6807
Catalytic asymmetric Diels–Alder reactions of N-allenoyloxazolidinones were investigated. Various chiral metal–bis(oxazoline) and metal–pyridinebis(oxazoline) complexes were screened. Cu(SbF6)2(H2O)2(t-BuBox) was found to be the most effective catalyst, giving the product in high yield, enantioselectivity, and endo:exo selectivity. The relative reactivity between N-allenoyloxazolidinones and N-alkenoyloxazolidinones was also investigated. A model for stereoinduction was proposed to account for the enantioselectivity and endo:exo selectivity. 相似文献
16.
Bräuer B Weigend F Fittipaldi M Gatteschi D Reijerse EJ Guerri A Ciattini S Salvan G Rüffer T 《Inorganic chemistry》2008,47(15):6633-6644
In this work we present the investigation of the influence of electronic and structural variations induced by varying the N,N'-bridge on the magnetic properties of Cu(II)- bis(oxamato) complexes. For this study the complexes [Cu(opba)] (2-) ( 1, opba = o-phenylene- bis(oxamato)), [Cu(nabo)] (2-) ( 2, nabo = 2,3-naphthalene- bis(oxamato)), [Cu(acbo)] (2-) ( 3, acbo = 2,3-anthrachinone- bis(oxamato)), [Cu(pba)] (2-) ( 4, pba = propylene- bis(oxamato)), [Cu(obbo)] (2-) ( 5, obbo = o-benzyl- bis(oxamato)), and [Cu(npbo)] (2-) ( 6, npbo = 1,8-naphthalene- bis(oxamato)), and the respective structurally isomorphic Ni(II) complexes ( 8- 13) have been prepared as ( (n)Bu 4N) (+) salts. The new complex ( (n)Bu 4N) 2[Cu(R-bnbo)].2H 2O ( 7, R-bnbo = (R)-1,1'-binaphthalene-2,2'- bis(oxamato)) was synthesized and is the first chiral complex in the series of Cu(II)-bis(oxamato) complexes. The molecular structure of 7 has been determined by single crystal X-ray analysis. The Cu(II) ions of the complexes 1- 7 are eta (4)(kappa (2) N, kappa (2) O) coordinated with a more or less distorted square planar geometry for 1- 6 and a distorted tetrahedral geometry for 7. Using pulsed Electron Nuclear Double Resonance on complex 6, detailed information about the relative orientation of the hyperfine ( A) and nuclear quadrupole tensors ( Q) of the coordinating nitrogens with respect to the g tensor were obtained. Electron Paramagnetic Resonance studies in the X, Q, and W-band at variable temperatures were carried out to extract g and A values of N ligands and Cu ion for 1- 7. The hyperfine values were interpreted in terms of spin population on the corresponding atoms. The obtained trends of the spin population for the monomeric building blocks were shown to correlate to the trends obtained in the dependence of the exchange interaction of the corresponding trinuclear complexes on their geometry. 相似文献
17.
Krumper JR Gerisch M Suh JM Bergman RG Tilley TD 《The Journal of organic chemistry》2003,68(25):9705-9710
A family of bis(oxazoline) complexes of coordinatively unsaturated monomeric rhodium(II) (2a,b, 3a,b) are described. These complexes serve as catalysts for cyclopropanation of olefins by ethyl diazoacetate, giving excellent yields (66-94%). Enantioselectivities for the cis product isomers are good (61-84%). The reaction shows an unusual preference for formation of the cis isomers. Catalytic aziridination of N-aryl imines with ethyl diazoacetate is also described. 相似文献
18.
Heteroleptic [Bis(oxazoline)](dipyrrinato)zinc(II) Complexes: Bright and Circularly Polarized Luminescence from an Originally Achiral Dipyrrinato Ligand 下载免费PDF全文
Dr. Julius F. Kögel Dr. Shinpei Kusaka Dr. Ryota Sakamoto Toshiki Iwashima Mizuho Tsuchiya Ryojun Toyoda Ryota Matsuoka Dr. Takamasa Tsukamoto Dr. Junpei Yuasa Prof. Dr. Yasutaka Kitagawa Prof. Dr. Tsuyoshi Kawai Prof. Dr. Hiroshi Nishihara 《Angewandte Chemie (International ed. in English)》2016,55(4):1377-1381
Heteroleptic zinc(II) complexes synthesized using achiral dipyrrinato and chiral bis(oxazoline) ligands show bright fluorescence with quantum efficiencies of up to 0.70. The fluorescence originates from the 1π–π* photoexcited state localized exclusively on the dipyrrinato ligand. Furthermore, the luminescence is circularly polarized despite the achirality of the dipyrrinato ligand. Single‐crystal X‐ray structure analysis discloses that the chiral bis(oxazoline) ligand undergoes intramolecular π–π stacking with the dipyrrinato ligand, inducing axial chirality in the dipyrrinato moiety. 相似文献
19.
A new bis(bidentate) azine ligand was prepared by linking (1Z,1′Z)-1,1′-{butane-1,4-diylbis[oxybenzene-4,1-diyl(1Z)ethyl-1-ylidene]}dihydrazine to salicylaldehyde. Two kinds of binuclear copper(II) and nickel(II) complexes with different
stoichiometries were prepared. Reaction of bis(azine) ligand with Cu(II) and Ni(II) acetate at a 1: 1 mole ratio gave double-stranded
binuclear bis(azine) complexes with stoichiometry [M(L)(H2O)2]2 containing [M(II)N2O2] centres while at a 2: 1 mole ratio, reaction of Cu(II) and Ni(II) chloride with bis(azine) resulted in dinuclear metal complexes
with the general stoichiometry [M2(L)Cl2(H2O)2]. Structures of the bis(azine) ligand and its complexes were identified by elemental analysis, IR and UV-VIS spectra, magnetic
susceptibility measurements, TGA, and powder XRD. Extraction properties of the bis(azine) ligand towards some transition metal
cations and dichromate anions were also reported. It was found that the bis(azine) ligand does not extract cations but it
has high extraction ability towards dichromate anions. 相似文献
20.
An efficient diastereo- and enantioselective Friedel-Crafts alkylation of indoles with 3-nitro-2H-chromenes catalyzed by diphenylamine-linked bis(oxazoline) and bis(thiazoline) Zn(II) complexes has been developed. This asymmetric Friedel-Crafts alkylation led to medicinally privileged indolyl(nitro)chromans in good yields with high enantioselectivities (up to 95% ee) and diastereoselectivities under mild reaction conditions. 相似文献