Fluorous solvents extractions

Reducing the number of fluorines on the fluorous tag also provides a general solution to the reaction solvent problem as the number of fluorines is reduced, the solubility in organic solvents tends to go up. Of course, the solubility in fluorous solvents tends to go down at the same time, and the residual tag must strike a balance between too many fluorines (low solubility in organic solvents) and too few fluorines (cannot easily be separated from organic compounds). However, thanks to the technique of fluorous solid-liquid extraction, there is surprisingly broad latitude here. 

The fluorous boronate is highly soluble in fluorous solvents, but when the nonfluorous R-group combines with another nonfluorous R-group the resulting product becomes preferentially soluble in the organic phase into which it is automatically extracted. 

From our cooperation partners. Profs. Gladysz and Dinjus, we received ligands with perfluorinated chains ( ponytails ), which show a thermomorphic solubility in organic solvents (P(et-Rf8)2(m-me-bz)) or maybe extracted with fluorous solvents (P(et-Rfs)3). P(et-Rf6)(z-pr)2 with only one perfluorinated... 

Otera has reported that fluorous distannoxanes such as 23, which dissociate to give Lewis acidic species, catalyze transesterifications in or-ganic/fluorous solvent mixtures [8,9]. Although 23 was insoluble in toluene at room temperature, it dissolved at reflux and efficiently promoted the transformation in reaction D of Scheme 4, as well as others. The catalyst precipitated upon cooling, but a fluorous solvent extraction was utilized for recovery (100%). Another thermomorphic fluorous Lewis acid catalyst was developed by Mikami [11]. He found that the ytterbium tris(sulfonamide) 24 could be used for Friedel-Crafts acylations imder homogeneous conditions in CICH2CH2CI at 80 °C, and precipitated upon cooHng to -20 °C (reaction E, Scheme 4). 

The enantioselective synthesis of a-amino acids employing easily available and reusable chiral catalysts or reagents presents clear advantages for large-scale applications. Accordingly, recyclable fluorous chiral phase-transfer catalyst 31 has been developed by the authors group, and its high chiral efficiency and reusability demonstrated in the asymmetric alkylation of 2. After the reaction, 31 could be easily recovered by simple extraction with FC-72 (perfluorohexanes) as a fluorous solvent and used for the next run, without any loss of reactivity and selectivity (Scheme 5.17) [23]. 

Larhed and coworkers employed fluorous triphenylphosphine as a ligand and Mo(CO)6 as a CO source for palladium-catalyzed hydrazidocarbonyla-tions of aryl iodides and bromides (Scheme 9) [36]. The fluorous ligand was recovered by extraction with fluorous solvent FC-84. 

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. 

In conclusion, we have successfully demonstrated that, by using a fluorous label and a fluorous solvent, we can affect the phase transfer of gold and CdSe nanoparticles from an aqueous or hydrocarbon medium to the fluorous phase. Single-walled carbon nanotubes and ZnO nanorods can be solubilized in a fluorous solvent after interaction with a fluorous amine. Phase transfer of the nanostructures to a fluorous solvent represents solubilization in a highly nonpolar solvent, accompanied by purification. The high nonpolarity of the fluorocarbon makes it possible to study the optical and other properties of nanostructures in a medium of very low refractive index. Since the fluorocarbon extracts only the species attached to the fluorous label, the process enables one to obtain solely one product in the pure state. We believe that fluorous chemistry may have practical utility in carrying out studies of nanostructures. 

The synthesis of array L7 is reported in Fig. 8.22. Compound 8.38 was reacted simultaneously with amines (Mi, two representatives), aldehydes (Mi, five representatives), and isonitriles (Ms, two representatives) to give 10 compounds (not all the combinations were reacted). The reaction was performed in trifluoroethanol (TFE), another hybrid fluorous-organic solvent (step a. Fig. 8.22), and after evaporation of the TFE, the crude product 8.39 was purified by two-phase extraction between fluorous solvents and benzene (step b). After evaporation of the solvent, the fluorous tag was cleaved with TBAF (step c) and a triphasic extraction (step d, Eig. 8.22) was performed to remove the fluorosilane tag and acid 8.38-related impurities extracted into the fluorous layer. Excess TBAE and TBAE-related impurities partitioned into the acidic aqueous layer. Yields and purities of the synthetic protocol are reported together with the structures of the library members L7a-j in Table 8.2. 

In addition to fluorous solvents and ionie liquids, supercritical fluids sc-fluids, scf s), sueh as supercritical carbon dioxide (se-C02), constitute a third class of neoteric solvents that can be used as reaction media. Although sc-fluids have been known for a long time and have been advantageously used as eluants in extraction and chromatography processes (see Sections A.6 and A.7 in the Appendix), their application as reaction media for chemical processes has become more popular only during the last decade. Some of their physical properties and the supercritical conditions necessary for their existence have already been described in Section 3.2 (see Figure 3-2 and Table 3-4) see also references [209, 211-220, 224-230] to Chapter 3 for reviews on sc-fluids and their applications (particularly for SC-CO2 and SC-H2O). 

One of the first examples of the use of fluorous solvents in reactions was their use in the extraction of photodegraded solid and liquid wastes contaminated with polychlorinated biphenyls (PCBs). Fluorinated ligands and scavengers... 

Recently a method has been described in the patent literature for the fractionation of essential oils using a fluorinated solvent.Oils studied included clove bud and bergamot, and fractionations could be performed in a semi-continuous mode. Fluorous solvents, as very non-polar media, offer an interesting alternative to the aqueous or alcoholic solvent approaches typically used in natural product extractions. However, it is unlikely that the technique will become widely used in this field. 

This can be exploited for the extractive separation of fluorous-tagged compounds from other substances. The partition coefficient depends on the size of the fluorous tag and on the organic solvent. The preference for the fluorous phase increases with increasing fluorine content and polarity of the organic phase. As the fluorous solvent, FC-72 (a mixture of CeFu isomers) is often used. At room temperature, it forms biphasic systems with solvents such as toluene, dichloromethane or acetonitrile and with aqueous media. Somewhat surprisingly, diethyl ether and tetrahydrofuran are good solvents for fluorous molecules and are miscible with FC-72 at... 

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