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1.
We report a highly efficient noncovalent immobilization of DNA fragments on surfaces by fluorous? fluorous interactions. The principle was applied to a simple and straightforward purification protocol for synthetic DNA. The method is completely compatible with standard solid‐phase synthesis of DNA. 相似文献
2.
Wen‐Bin Yi 《合成通讯》2013,43(20):2957-2961
Ytterbium perfluorooctanesulfonate [Yb(OPf)3] and perfluorooctanesulfonic acid [PfOH] catalyze the highly efficient dinitration of toluene, benzene, benzyl chloride, and chlorobenzene in fluorous media. Notably the process produces almost no waste acid, as opposed to the traditional case. The fluorous phase‐containing catalyst could be easily and efficiently recovered for reuse by simple phase separation. 相似文献
3.
Mark C. McCairn 《Tetrahedron letters》2008,49(8):1328-1330
Microwave-promoted synthesis and fluorous purification procedures have been employed successfully to generate 4-(tetrathienyl)butyric acid rapidly. Initially, a fluorous tag 1H,1H-perfluorooctylamine was tethered to 4-(thienyl)butyric acid via an amide traceless linkage. Subsequent, sequential α-bromination and Stille cross-coupling reactions with 2-(tributylstannyl)thiophene grew the fluorous-tagged 4-(oligothienyl)butyric acid efficiently. Each synthetic transformation was followed by a fluorous-solid phase extraction procedure to isolate the fluorous-tagged compound intermediate in excellent yield. Finally, the fluorous tag was cleaved by microwave-promoted saponification of the amide bond to liberate the desired 4-(tetrathienyl)butyric acid. 相似文献
4.
In fluorous biphase system, metal bis(perfluorooctanesulfonyl)amides are better Lewis acid catalysts than the analogous triflates toward either transesterifications, or direct esterifications, or Friedel-Crafts acylations or Baeyer-Villiger oxidations. These catalysts are selectively soluble in lower fluorous phase and can be recovered simply by phase separation. Furthermore, these catalysts can be reused without decrease of activity in most cases. 相似文献
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6.
Low partition coefficients of fluorous components have been a persistent problem in liquid-liquid separations using perfluoroalkanes as the fluorous phase. Solvent tuning of both the nonfluorous and the fluorous phase dramatically enhances the partitioning of light or polar fluorous molecules into the fluorous liquid phase, while minimally effecting partition coefficients of nonfluorous molecules. These findings suggest an expanded scope for liquid-based separations in fluorous biphasic catalysis, fluorous-tagged reagents, fluorous-supported oligomer synthesis, and related areas. [reaction: see text] 相似文献
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8.
Bergbreiter DE Franchina JG Case BL Williams LK Frels JD Koshti N 《Combinatorial chemistry & high throughput screening》2000,3(2):153-164
Fluorous phase soluble polymer supports derived from fluoroacrylate polymers are described. N-Acryloxysuccinimide-containing fluoroacrylate polymers were readily prepared from commercially available monomers. The activated acrylates so prepared were then converted into chelating and non-chelating ligands by amidation of the N-acryloxysuccinimide active ester residues. Phosphine ligands attached to these supports were used to prepare neutral and cationic rhodium(I) hydrogenation catalysts as well as palladium(0) catalysts. Similar substitution of pendant active ester groups to form hydroxamic acid ligands for metal sequestration is also feasible. Liquid/liquid extraction readily separated, recycled and reused these polymer-bound ligands and catalysts. While fluorous phase solubility could be attained with polymers containing only heptafluorobutyryl groups, selective solubility in a fluorous phase in contact with an organic phase was only seen with fluoroacrylates that contained larger fluorinated ester groups. 相似文献
9.
Fluorous-tagged compounds can rapidly be separated from organic (non-tagged) compounds by the new separation technique of reverse fluorous solid-phase extraction (r-fspe). In a reversal of the roles of solid and liquid phases in standard fluorous spe, a mixture is charged to a polar solid phase (standard silica gel) and then eluted with a fluorous solvent or solvent mixture. The organic components of the mixture are retained, while the fluorous components pass. [structure: see text] 相似文献
10.
A novel approach to the preparation of perfluorotail-functionalized triarylphosphines using a p-silyl substituent as the branching point has been developed. This approach enabled the attachment of between three and nine perfluorotails per phosphorus atom, resulting in the production of highly fluorous tris[p-(1H,1H,2H, 2H-perfluoroalkylsilyl)aryl]phosphines, P[C(6)H(4)-p-SiMe(3)(-)(n)()(CH(2)CH(2)C(x)()F(2)(x)()(+1))(n)()](3) (n = 1, 2, 3; x = 6, 8), containing between 50 and 67 wt % fluorine. (31)P NMR studies indicate that the phosphorus atoms, and consequently the sigma-donor and pi-acceptor properties of these phosphines, are not influenced by the electron-withdrawing perfluoroalkyltails. The fluorous triarylphosphines are readily soluble in fluorous solvents and display fluorous phase preference in several fluorous biphasic systems. The phase partitioning of these fluorous ligands, as well as their donor properties, is discussed in relation to their potential for fluorous biphasic catalyst separation. 相似文献
11.
Masato Matsugi Misaki Suganuma Shoko Yoshida Shohei Hasebe Yoko Kunda Kotaro Hagihara Sayaka Oka 《Tetrahedron letters》2008,49(46):6573-6574
A convenient methodology for the separation of a fluorous by-product using fluorous chemistry is described. A Mukaiyama coupling reagent bearing a medium fluorous tag, between 40% and 60% fluorine by weight, can be effectively separated from non-fluorous components by increasing the water content of the crude reaction mixture and subsequent filtration. Additional fluorous solid phase extraction is not necessary. 相似文献
12.
Novel prolinol carrying two perfluorohexylethyl groups at the α-position was prepared from l-proline as a starting chiral substrate. Catalytic asymmetric reduction of various ketones, including mono-, di-, and trifluoromethylated acetophenones, using fluorous oxazaborolidines derived from fluorous prolinol afforded the corresponding alcohols in good to excellent yields and with high enantioselectivities (up to 93.2% ee). The fluorous prolinol was recovered without any fluorous solvents or silica gel by simply cooling the organic phase and filtration. 相似文献
13.
Lipase-catalyzed acylation of racemic alcohols with a highly fluorinated acyl donor allows their kinetic resolution accompanied by the simultaneous enantiomer-selective fluorous phase labeling. Both the tagged and the untagged enantiomer can be separated without chromatography by a very efficient partition between a fluorous and an organic phase. The method has been successfully applied to the resolution of typically racemic secondary alcohols of low molecular weight. The fluorous label can be recovered quantitatively. 相似文献
14.
Masaru Kojima 《Tetrahedron letters》2007,48(25):4431-4436
A new fluorous benzylidene acetal protecting group was regioselectively introduced into carbohydrates, deprotected under acidic conditions, and reused. Oligosaccharides were synthesized via regioselective conversion of the fluorous acetal group to the benzyl group by traditional reaction conditions. The fluorous compounds were easily separated from non-fluorous by-products by fluorous solid phase extraction. 相似文献
15.
A novel fluorous tagging-detagging strategy has been developed featuring a fluorination as the detagging process; fluorous allylsilanes were prepared by cross-metathesis and subsequently subjected to electrophilic fluorodesilylation; Selectfluor was used as the detagging reagent; the resulting allylic fluorides were successfully purified by fluorous solid phase extraction. 相似文献
16.
[reaction: see text] A series of asymmetric free-radical-mediated intermolecular conjugate additions using a fluorous oxazolidinone chiral auxiliary has been completed. The fluorous auxiliary facilitated product isolation using fluorous solid phase extractions (FSPE), effectively removing excess organic and organometallic reagents. Parallel reactions carried out with a similar but nonfluorous norephedrine-derived oxazolidinone demonstrated the superior stereoselectivity and purification obtainable with the fluorous chiral auxiliary. 相似文献
17.
Practical syntheses of new triarylphosphines bearing both linear and branched fluorous tags (Rf) are reported. The phosphines have one, two, or all three aryl rings bearing fluorous tags: (Ph)(3)(-)(n)()P(C(6)H(4)(CH(2))(m)()Rf)(n)(). Fluorous-organic partition coefficients have been measured and the retention properties of both the phosphines and the derived phosphine oxides on fluorous reverse phase silica have been studied. While applications relying on liquid-liquid extractive separations of these phosphines may be limited to those bearing three fluorous chains, the technique of solid phase extraction should be broadly applicable to phosphines, phosphine oxides, and derived metal complexes. A parallel platinum-catalyzed allylation of aldehydes with fluorous allyl stannanes illustrates the usefulness of the new fluorous ligands in small-scale synthesis. 相似文献
18.
Fluorous chemistry, involving the use of a fluorous label for the functionalization of a substrate and a fluorous solvent for extraction of the functionalized substrate, is shown to be effective in solubilizing gold and CdSe nanoparticles in a fluorous medium, through phase transfer from an aqueous or a hydrocarbon medium. While these nanoparticles were functionalized with a fluorous thiol, single-walled carbon nanotubes and ZnO nanorods could be solubilized in a fluorous medium by reacting them with a fluorous amine. Fluorous chemistry enables the solubilization of the nanostructures in the most nonpolar liquid medium possible. 相似文献
19.
Structure assignment of lagunapyrone B by fluorous mixture synthesis of four candidate stereoisomers
Techniques of fluorous mixture synthesis have been used to make four candidate stereoisomers for the natural product lagunapyrone B. A quasiracemic mixture of vinyl iodides whose component configurations at C19-21 were encoded by fluorous silyl groups was fused to a central fragment by a Negishi coupling. A separate quasiracemic mixture of pyrone fragments whose component configurations at C6,7 were also encoded by fluorous silyl groups was synthesized and demixed. Stille coupling of the resulting pure quasienantiomers with the quasiracemic mixture provided two quasi-diastereomeric samples, which were demixed and detagged to provide all four lagunapyrone B stereoisomers. Lagunapyrone was assigned the 6R,7S,19S,20S,21R configuration by comparison of optical rotations. 相似文献
20.
Christopher J. Wilson Daniela A. Wilson Andrew E. Feiring Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2010,48(11):2498-2508
Traditionally the fluorous phase is generated with perfluorinated alkyl groups that are usually perfluorooctyl or longer and are bioaccummulative and biopersistent and therefore, are considered environmentally unfriendly. Here we report a new concept for the construction of the fluorous phase. This concept is based on the amplification of the fluorous effect with the help of dendritic architectures containing very short semifluorinated groups on their periphery. This new concept was demonstrated by the convergent synthesis of the first and second generation AB3 and AB2 benzyl ether dendrons functionalized on their periphery via catalytic nucleophilic addition of their phenolates to perfluoropropyl vinyl ether. The resulting dendrons are liquids. Their fluorous phase affinity was analyzed and demonstrated that the dendritic architecture amplifies the fluorous phase at a specific generation by the number of functional groups on the dendron periphery, and at different generations by increasing their generation number. Therefore, this concept is very efficient for the design and synthesis of new fluorous materials. In addition, by contrast with dendrons containing perfluoroalkyl groups on their periphery, the current dendrons mediate the disassembly of their parent building blocks but do not mediate the self‐assembly in a supramolecular architecture. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2498–2508, 2010 相似文献