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1.
Prof. Dr. Christer B. Aakeröy Dr. Michele Baldrighi Dr. John Desper Prof. Dr. Pierangelo Metrangolo Prof. Dr. Giuseppe Resnati 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(48):16240-16247
Through a combination of structural chemistry, vibrational spectroscopy, and theory, we have systematically examined the relative structure‐directing importance of a series of ditopic halogen‐bond (XB) donors. The molecular electrostatic potential surfaces of six XB donors were evaluated, which allowed for a charge‐based ranking. Each molecule was then co‐crystallized with 21 XB acceptors and the results have made it possible to map out the supramolecular landscape describing the competition between I/Br–ethynyl donors, perfluorinated I/Br donors, and I/Br–phenyl based donors. The results offer practical guidelines for synthetic crystal engineering driven by robust and directional halogen bonds. 相似文献
2.
Grayson EJ Ward SJ Hall AL Rendle PM Gamblin DP Batsanov AS Davis BG 《The Journal of organic chemistry》2005,70(24):9740-9754
[reaction: see text] Glycosyl disulfides have been shown for the first time to be effective glycosyl donors. Glucosylation and galactosylation of a panel of representative alcohol acceptors allowed the formation of 28 simple glycosides, disaccharides, and glycoamino acids in yields of up to 90%. As well as providing a novel class of effective glycosyl donors, the ability to easily alter the nature of the aglycon and the ability to differently activate donors that differ only in their aglycon simply through altering conditions lends glycosyl disulfide donors to their use in latent-active reactivity tuning strategies. 相似文献
3.
N'-Glycopyranosylsulfonohydrazides are introduced as glycosyl donors for protecting group free synthesis of O-glycosides, glycosyl azides, and oxazolines. Mono- and disaccharides containing a reducing terminal N-acetylglucosamine residue were condensed with p-toluenesulfonylhydrazide to give the desired beta- d-pyranose donors. These donors can be activated with NBS and then glycosidated with the desired alcohol or transformed to the oxazoline or glycosyl azide. 相似文献
4.
Maria Carmela Sacchi Fabrizio Forlini Incoronata Tritto Paolo Locatelli 《Macromolecular Symposia》1995,89(1):91-100
The results of a study on a new generation of MgCl2 supported Ziegler-Natta catalysts that contain dialkyl propane diethers as internal donors and produce highly stereospecific polypropene even without any external donor are presented. The results concerning three different catalysts containing 2,2-diisobutyl-1,3-dimethoxy propane (DIBDMP), 2,2-dicyclopentyl-1,3-dimethoxy propane (DCPDMP) and 2-ethyl,2-butyl-1,3-dimethoxy propane (EBDMP) as internal donors are compared. The same donors have also been studied by using them as external donors with a catalyst contaning diisobutyl phthalate as internal donor. The present results, along with previously obtained findings on traditional supported Ziegler-Natta catalysts, permit a general comprehension of the role of internal and external donors. 相似文献
5.
Simon Rohrbach Dr. Rushabh S. Shah Prof. Dr. Tell Tuttle Prof. Dr. John A. Murphy 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(33):11576-11580
Neutral organic super electron donors (SEDs) display impressive reducing power but, until now, it has not been possible to use them catalytically in radical chain reactions. This is because, following electron transfer, these donors form persistent radical cations that trap substrate‐derived radicals. This paper unlocks a conceptually new approach to super electron donors that overcomes this issue, leading to the first catalytic neutral organic super electron donor. 相似文献
6.
Oakes DC Kimberley BS Gibson VC Jones DJ White AJ Williams DJ 《Chemical communications (Cambridge, England)》2004,(19):2174-2175
Group 4 metal complexes containing phenoxy-amide ligands bearing soft pendant donors are shown to give more highly active ethylene polymerisation catalysts than counterparts containing hard donors or systems without a pendant donor. 相似文献
7.
Reported herein is a new protocol for glycosidation of alkyl and aryl thioglycosides in the presence of copper(II) bromide. While the activation with CuBr2 alone was proven suitable for reactive glycosyl donors, the activation of less reactive donors was more efficient in the presence of triflic acid as an additive. A variety of thioglycoside donors in reactions with different glycosyl acceptors were investigated to determine the initial scope of this reaction. 相似文献
8.
Kwang Bo Chung Masao Tomoi 《Journal of polymer science. Part A, Polymer chemistry》1992,30(6):1089-1097
Crown ethers bound to microporous polystyrene resins by oxyethylene spacers were prepared by the reaction of monoazacrown ethers with 2-tosyloxyethoxymethylated or 2-(2-tosyloxyethoxy)ethoxymethylated polystyrene resins crosslinked with 2 mol % of divinylbenzene. The activity of the immobilized lariat crowns for halogen exchange reactions under triphase conditions has been studied as a function of catalyst structure, loading, substrate structure, reagent structure, and solvent. The lariat catalysts with extra oxygen donors in the spacer chain exhibited higher activity than the corresponding immobilized catalysts without the donors in the spacer. The increased activity of the catalyst containing 15-crown-5 unit and two extra donors for the reaction of 1-bromooctane with KI was concluded to result from the enhanced complexation with the K+ ion, induced by the cooperative coordination of the crown unit donors and the donors in the spacer chain. The recovered catalysts could be re-used without decrease in activity. 相似文献
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10.
An amine mono(phenolate) ligand bearing two side-arm donors led to octahedral trialkoxo and trialkyl group IV metal complexes, in which one of the donors was unbound, and to exceptionally stable cationic complexes in which the two side-arm donors were tightly bound. 相似文献
11.
5-Thioglucosylation of a 1,6-anhydro-2-azido-2-deoxy-β-d-glucopyranose derivative was carried out with various 1,5-dithioglucosyl donors. The use of per-O-acetyl donors resulted in poor yields of an α-disaccharide. On the other hand, per-O-benzyl donors selectively gave an α-disaccharide in good to excellent yields regardless of the anomeric configuration of the donors. To study the relevance of the glycosylation results to the pre-equilibrium of exo- versus endocyclic sulfide activation, the relative nucleophilicities of exo- and endocyclic sulfides were estimated from the regioselectivities in the electrophilic oxidation of the per-O-benzyl donors with m-chloroperbenzoic acid. The results obeyed stereoelectronic effects and the endocyclic sulfides were more nucleophilic than the exocyclic sulfides for both anomers of per-O-benzyl-1,5-dithioglucosyl donors, the relative nucleophilicities of the endocyclic over exocyclic sulfides being 67% and 100%, respectively, for the α- and β-anomers. The results of the glycosidation and oxidation suggest that the glycosidation proceeded through an exocyclic cleavage mechanism despite the preferential endocyclic activation of 1,5-dithioglucosides. 相似文献
12.
Walvoort MT de Witte W van Dijk J Dinkelaar J Lodder G Overkleeft HS Codée JD van der Marel GA 《Organic letters》2011,13(16):4360-4363
The reactivity of a variety of mannopyranosyl uronic acid donors was assessed in a set of competition experiments, in which two (S)-tolyl mannosyl donors were made to compete for a limited amount of promoter (NIS/TfOH). These experiments revealed that the reactivity of mannuronic acid donors is significantly higher than expected based on the electron-withdrawing capacity of the C-5 carboxylic acid ester function. A 4-O-acetyl-β-(S)-tolyl mannuronic acid donor was found to have similar reactivity as per-O-benzyl-α-(S)-tolyl mannose. 相似文献
13.
Multiple Multidentate Halogen Bonding in Solution,in the Solid State,and in the (Calculated) Gas Phase
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Stefan H. Jungbauer Severin Schindler Dr. Eberhardt Herdtweck Prof. Dr. Sandro Keller Prof. Dr. Stefan M. Huber 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(39):13625-13636
The binding properties of neutral halogen‐bond donors (XB donors) bearing two multidentate Lewis acidic motifs toward halides were investigated. Employing polyfluorinated and polyiodinated terphenyl and quaterphenyl derivatives as anion receptors, we obtained X‐ray crystallographic data of the adducts of three structurally related XB donors with tetraalkylammonium chloride, bromide, and iodide. The stability of these XB complexes in solution was determined by isothermal titration calorimetry (ITC), and the results were compared to X‐ray analyses as well as to calculated binding patterns in the gas phase. Density functional theory (DFT) calculations on the gas‐phase complexes indicated that the experimentally observed distortion of the XB donors during multiple multidentate binding can be reproduced in 1:1 complexes with halides, whereas adducts with two halides show a symmetric binding pattern in the gas phase that is markedly different from the solid state structures. Overall, this study demonstrates the limitations in the transferability of binding data between solid state, solution, and gas phase in the study of complex multidentate XB donors. 相似文献
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[reaction: see text] A new method for the synthesis of alpha(2 --> 9) oligosialic acids is developed using phosphite sialyl donors that are protected with a C-5 N-trifluoroacetyl (NHTFA) substituent. Compared with conventional donors, these donors gave a higher degree of alpha-anomeric selectivity during glycosidic bond formation and better yields during iterative sialylation in the synthesis of oligosialic acids. 相似文献
16.
The highly stereocontrolled synthesis of the 3-amino-3-deoxy-beta-mannopyranosides is achieved by means of thioglycoside donors protected with a 4,6-O-benzylidene or alkylidene acetal and a benzylidene imine group. Among the various nitrogen protecting groups investigated only the Schiff's base was found to give high beta-selectivity. N-Phthalimido and N-acetamido protected donors were found to be highly alpha-selective, whereas 3-azido-3-deoxy glycosyl donors gave intermediate selectivity. The reasons for the protecting group dependency are discussed in terms of the change in the O2-C2-C3-N3 torsional interaction on conversion of the covalent glycosyl triflates to the transient oxacarbenium ions. 相似文献
17.
The formation constants of mixed-ligand complexes with hetero donors of the type CuAB where A is a carboxylic acid such as
lactic acid or oxalic acid and B is an α−or β-amino acid are studied by polarography. The mixed-ligand stabilisation constant
clearly indicates the preferred formation of copper(II) mixedligand complexes with hetero donors over homo donors. The other
driving forces leading to the favoured formation of mixed-ligand complexes are also discussed. 相似文献
18.
Sang Yull Kim Yuichi Hiraoka Toshiaki Taniike Minoru Terano 《Macromolecular Symposia》2009,285(1):115-120
Effects of external donor induced direct contact without alkylaluminum were studied for Ziegler-Natta catalysts containing monoester and diester as internal donors on the catalytic performances such as activity and stereoselectivity. Traditional slurry polymerizations were carried out for rather short period after direct contact for a variety of time. GC analysis was also performed to observe replacement phenomena of donors during direct contact. It was postulated that the different performances of the catalysts were greatly affected by the pair of internal and external donors. 相似文献
19.
Gordiyenko OI Gordiyenko YE Makedonska VO 《Bioelectrochemistry (Amsterdam, Netherlands)》2004,62(2):119-122
The densities of cell distributions by spherical index (SI) in erythrocyte populations from healthy adults and donors with endocrine pathologies were determined via the developed method. The investigation shows that this characteristic varies for different donors, thereby reflecting the erythrocyte population state of an individual donor. Individual distribution curves obtained from healthy donors are close to Gaussian and are characterized by smooth curve plot with one maximum. Cells distribution by SI in donors with endocrine pathologies has a polymodal character. Our research shows that the developed method for determining erythrocyte distribution density by SI is a sensitive and informative test for quantitative evaluation of an erythrocyte population state. Moreover, this characteristic has clear physical and physiological significance, because an erythrocyte shape is strongly conditioned by the cell age and influences the ability to pass through microcapillaries in blood circulation. 相似文献
20.
New bifunctional organocatalysts amine-thioureas bearing multiple hydrogen bonding donors were synthesized and applied in catalytic asymmetric Michael addition of acetylacetone to aryl and alkyl nitroolefins. Multiple hydrogen bonding donors play a significant role in accelerating reactions, improving yields and enantioselectivities. 相似文献