Modifying tempo

A double mediatory system consisting of modified TEMPO and halide ion or metal ion was also exploited for the oxidation of alcohols [53-55]. A number of carbohydrates have been chemoselectively oxidized at the primary hydroxyl group to uronic acids [56]. 

A copper catalysed click (azide-alkyne cycloaddition) reaction has been used to prepare a fluorous-tagged TEMPO catalyst (Figure 7.20). TEMPO is a stable organic free radical that can be used in a range of processes. In this case, its use in metal-free catalytic oxidation of primary alcohols to aldehydes using bleach as the terminal oxidant was demonstrated. The modified TEMPO can be sequestered at the end of the reaction on silica gel 60 and then released using ethyl acetate for reuse in further reactions in this way the TEMPO was used four times with no loss in activity. 

The polymerization of VAc by NMP was reported by Matyjaszewski group in 1996. To reduce the bimolecular radical termination dnring the polymerization, the authors attached the stable nitroxyl radical (TEMPO 2,2,6,6-tetramethylpiperidine-l-oxyl radical) to the interior of a dendrimer and used this modified TEMPO ([G-3]-TEMPO) as a scavenger combined with 2,2 -azobis(2-methyl-propionitrile) (AIBN) to polymerize VAc. Fignre 5 shows the kinetic plot and the dependence of molecular weight on monomer conversion for the bnlk polymerization of VAc at 80 °C in the presence of [G-3]-TEMPO/AIBN. 

A number of modifications were made to meet scale-up requirements. In the preparation of the common intermediate, LiBH4 was used in place of LiAlH4 in Step A-2 and a TEMPO-NaOCl oxidation was used in place of Swern oxidation in Step A-3. Some reactions presented difficulty in the scale-up. For example, the boron enolate aldolization in Step B-l gave about 50% yield on the 20- to 25-kg scale as opposed to greater than 75% on a 50-g scale. The amide formation in Step B-3 was modified to eliminate the use of trimethylaluminum, and the common intermediate 17 could be prepared on a 30-kg scale using this modified sequence. The synthesis of the C(l)-C(6) segment V was done by Steps C-l to C-5 in 66% yield on the scale of several kg. 

This blend was obtained by polymers mixture extrusion and extraction with the azeotropic mixture of hexane/ethanol, and modifying the obtained polymer surface by coupling of 4-isocyanato butanoic acid methyl ester (as a spacer molecule) to PVA blend, saponification of methyl ester groups and coupling of 4-amino-TEMPO (2,2,6,6-tetramethylpiperidine-l-oxyl) [229],... 

TEMPO has been structurally modified to bring about new selectivities [49, 50]. 

As a result, a highly enantioselective oxidation of (22) was achieved by using a TEMPO-modified graphite felt electrode in the presence of (—)-sparteine, where the enantiopurity of the remaining (22) was >99% and the current efficiency for (23) was >90% (Scheme 8) [51]. However, this selectivity has been questioned [52]. 

MeCN, NaCI04 TEMPO-modified graphite felt anode... 

Coupling A graphite felt electrode chemically modified with TEMPO led to the enantioselective electrocatalytic coupling of 2-naphthol, 2-methoxynaphth-alene and 10-hydroxyphenanthrene with high enantioselectivity (up to 98% ee) in the presence of (-)-sparteine as a chiral base [366]. 

In an enantiomer-differentiating oxidation at a poly-(L-valine)-coated Pb02 anode, rac-2,2-dimethyl-l -phenyl-1 -propanol was partially oxidized leaving 43% optically pure (5)-alcohol [371]. At a TEMPO-modified graphite felt anode rac-1-phenyl-ethanol has been enantioselectively oxidized in the presence of (-[-sparteine leaving 46% of the (/ [-alcohol with 99.6% ee [372]. However, under the same conditions, an exclusive dehydrogenation of (-[-sparteine to the iminium salt without oxidation of the alcohol was found [373]. 

Some successful attempts to immobilize catalysts for the oxidation of alcohols to carbonyl compounds involve the attachment of TEMPO-derivatives to a solid phase. Bolm et al. were the first to immobilize l-hydroxy-2,2,6,6-tetramethylpiperi-dine to modified silica gel (SG-TMP-OH) (11) and applied in the oxidation of multifunctional alcohols [68]. Other groups further investigated the use of polymer-supported TEMPO [69]. This system allowed the oxidation of alcohols to aldehydes and ketones, respectively, using bleach to regenerate the immobilized ni-troxyl radical (Scheme 4.6). 

TEMPO has been structurally modified to bring about new selectivities. Highly efficient anionic water-soluble TEME<), oil-in-water nanoemulsion containing TEME for oxidation of alcohols and a waste-free system were developed. Especially, the sterically less crowded azabicyclo-Af-oxyls oxidized /-menthol to Z-menthone with much higher efficiencies than TEME O (equation 23). ... 

Tetramethylpiperidin-1-oxyl radical (TEMPO) immobilized on aminopropyl-modified silica gel... 

E. M. Belgsir and H. J. Schafer, Selective oxidation of carbohydrates on Nafion -TEMPO-modified graphite felt electrodes, Electrochem. Commun., 3 (2001) 32-35. 

Frechet and coworkers recently described how living free radical polymerization can be used to make dendrigrafts. Either 2,2,6,6-tetramethylpiperidine oxide (TEMPO) modified polymerization or atom transfer radical polymerization (ATRP) can be used [96] (see Scheme 10). The method requires two alternating steps. In each polymerization step a copolymer is formed that contains some benzyl chloride functionality introduced by copolymerization with a small amount of p-(4-chloromethylbenzyloxymethyl) styrene. This unit is transformed into a TEMPO derivative. The TEMPO derivative initiates the polymerization of the next generation monomer or comonomer mixture. Alternatively, the chloromethyl groups on the polymer initiate an ATRP polymerization in the presence of CulCl or CuICl-4,4T dipyridyl complex. This was shown to be the case for styrene and n-butylmethacrylate. SEC shows clearly the increase in molecu-... 

TEMPO-modified poly(ethylene-co-propylene-g-maleic anhydride), (IV), and poly((ethylene-co-1 -decene)-g-alkylacrylates), (V), were prepared by Matsugi [3] and used as polymer blend compatibilizing agents. 

The antiapoptopic protein Bcl-xL is responsible for the reduced susceptibility of cancer cells to undergo apoptosis and is therefore a target for the development of new anticancer agents. The structure of a previously identified ligand for Bcl-xL (39) was modified to incorporate a TEMPO spin label (40). By use of spin-labeled (40), an eight-compound library was screened for simultaneous binding to Bcl-xL. From this library an aromatic ketoxime... 

Osa and coworkers [405,466] developed a graphite felt electrode modified with 2,2,6,6-tetramethylpiperidin-l-yloxyl (TEMPO) and applied it to enantioselective, electro-catalytic oxidative coupling of naphthol, naphthyl ether, and phenanthrol in the presence of (—)-sparteine as a base. The enantioselectivity of the coupling products were as high as 98%. 

Recently, Osa and coworkers [502] have reported highly enantioselective electroca-talytic oxidation of racemic monoalcohols using a TEMPO-modified graphite felt electrode in the presence of (—)-sparteine. Optically almost pure i -isomeric alcohols remained unreacted. Highly enantioselective lactonization of racemic diols was also achieved by using the same TEMPO-modified electrode to give (S)-isometric lactones [503]. 

Abstract Cellulose is the most important biopolymer in Nature and is used in preparation of new compounds. Molecular structure of cellulose is a repeating unit of p-D-glucopyranose molecules forming a linear chain that can have a crystallographic or an amorphous form. Cellulose is insoluble in water, but can dissolve in ionic liquids. Hemicelluloses are the second most abundant polysaccharides in Nature, in which xylan is one of the major constituents of this polymer. There are several sources of cellulose and hemicelluloses, but the most important source is wood. Typical chemical modifications are esterifications and etherifications of hydroxyl groups. TEMPO-mediated oxidation is a good method to promote oxidation of primary hydroxyl groups to aldehyde and carboxylic acids, selectively. Modified cellulose can be used in the pharmaceutical industry as a metal adsorbent. It is used in the preparation of cellulosic fibers and biocomposites such as nanofibrils and as biofuels. 

TEMPO-mediated oxidation. With regenerated and mercerized celluloses, the oxidation leads to water-soluble p-l,4-linked poly glucuronic acid sodium salt (cellouronic acid, CUA) quantitatively [16]. In contrast, with native celluloses having the cellulose I crystal structure, the cellulose slurries maintain the slurry states even after TEMPO-mediated oxidation. These modified celluloses form water-insoluble fibers [17]. This has enabled modification of the surface of cellu-losic fibers. 

It was speculated that the second step of over-oxidation to acid might take place via a free radical pathway, arising from the catalytic decomposition of the t-BuOOH. It was further thought that the use of a free radical inhibitor might reduce the extent of the acid formation and inqjrove the overall aldehyde selectivity. The use of free radical scavengers such as 2,6-di-ier/-butyl-4-methylphenol (Table 4, Run 24), the stable free-radical, TEMPO, (Run 25) or the amine type inhibitor, N-Phenyl -2-Naphthylamine (Run 26), did not show any improvement in the reaction selectivity towards the formation of the aldehyde. The lack of any significant reduction in the amoimts of ester formed when using these modifiers showed that both steps of aldehyde and acid formation most likely do not include the involvement of free radical intermediates. 

The modification of electrodes with PVC membranes has found applicability in ion selective electrode work [99] (so-called "coated wire electrode ). The molecular motion of species within such electrodes has been investigated by Compton and Waller [100]. Using a range of derivatives of the nitroxide spin probe TEMPO, they were able to show how the rotational correlational time was dependent upon the molecular volume of the probe and, by use of variable-temperature apparatus, how this varied with temperature. The effect of various plasticizers upon the molecular motion within the PVC membrane was investigated, rotational correlational times being dependent upon the nature of the plasticizer and the loading level. The effect of loading level upon the correlation time was shown to correlate with data obtained by Compton Maxwell [101] for the response times of K+ ion selective electrodes based upon PVC modified electrodes. 

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