Alkenes solid support

Chemistry on solid support has gained tremendous importance during the last few years, mainly driven by the needs of the pharmaceutical sciences. Due to the robust and tolerable nature of the available catalysts, metathesis was soon recognized as a useful technique in this context. Three conceptually different, RCM-based strategies are outlined in Fig. 11. In the approach delineated in Fig. 1 la, a polymer-bound diene 353 is subjected to RCM. The desired product 354 is formed with concomitant traceless release from the resin. This strategy is very favorable, since only compounds with the correct functionality will be liberated, while unwanted by-products remain attached to the polymer. However, as the catalyst is captured in this process by the matrix (355), a higher catalyst loading will be required, or ancillary alkenes have to be added to liberate the catalyst. 

The utilization of solid-support pyridinium salts in the synthesis of bicyclic pyridines has been reported. Yue et al. synthesized 1,2,3,7-tetrasubstituted indolizines using poly(ethyleneglycol)bound pyridinium salts <06JHC781>. The PEG-bound pyridinium salts 53 were reacted with alkenes or alkynes in the presence of Et3N, via 1,3-dipolar cycloaddition, to give polymer-bound indolizines 54 and 55, respectively. Liberation of the heterocycle with KCN/MeOH afforded 1,2,3,7-tetrasubstituted indolizines 56 and 57 in good to excellent yield. 

Olefinations using a solid-supported triphenylphosphine were accomplished within 5 min of microwave heating at 150 °C using potassium carbonate as the base and methanol as the solvent (Scheme 7.96). A variety of aldehydes and organic halides were studied with the solid-supported phosphine, yielding the corresponding alkenes in excellent purities. 

The examples listed in Table 3.21 illustrate the synthetic possibilities of cross metathesis. In many of the procedures reported, advantage is taken of the fact that some alkenes (e.g. acrylonitrile, styrenes) undergo slow self metathesis only. Interestingly, it is also possible to realize cross metathesis between alkenes and alkynes (Table 3.21, Entries 11-13), both in solution and on solid supports [927,928]. 

Recently, the semi-synthesis of Vancomycin (48) on solid supports was accomplished using an allylic linker (Scheme 3.2) [123, 124]. Polymer-bound chiral electrophilic selenium reagents have been developed and applied to stereoselective se-lenylation reactions of various alkenes (Tab. 3.9) [125]. 

C-C bond formation using the Heck reaction allows the introduction of functional groups to obtain new organic structures on solid supports. This reaction between an alkene with an alkenyl or an aryl halide has been widely employed in various in-tra- and inter-molecular versions on solid-phase because of the readily accessibility of starting materials. The Heck reaction was performed on immobilized aryl or alkenyl halides with soluble alkenes and vice versa (Scheme 3.11). 

For the Grieco three component reaction it is also possible to coimect the aldehyde [283] or the alkene [284] to the solid support. 

Oxidations of various organic functional groups such as alcohols or alkenes are some of the most important transformations in organic chemistry. Unfortunately, their use is sometimes restricted hy poor selectivities or the need for transition metals and other species, which might be toxic or difficult to remove during work-up. Therefore, numerous attempts have been made to immobihze oxidants on a solid support [4], and these are compiled in the following. 

The first examples of an electrostatie attachment of POMs on solid supports are dated to the mid 1980. Baba et al. reported immobilization of heteropolyacids on the anion-exchange resin Amberlist-15 [68]. Later on, this type of the support was successfully used by Jacob s group to immobilize the Venturello complex P04[W0(02)2]4, well known as highly selective homogeneous catalyst for H202-based epoxidation of alkenes... 

Blechert reported a skillful method of cross-enyne metathesis. Solid-supported alkyne 139 is reacted with alkene in the presence of Ic to give 140. For cleavage of 1,3-diene from solid-supported product 140 having an allyl acetate moiety, palladium-catalyzed allylic substitution is used. Thus, 140 is treated with Pd(PPh3)4 in the presence of methyl malonate to afford three-component coupling product 141 in good yield ... 

Quantitative Knoevenagel condensations of aldehydes with active methylene compounds are most desirable due to the frequent use of the electron-poor alkenes that arise [107]. But previous techniques use catalysts and produce dangerous wastes even if highly energy-consuming microwave irradiation upon polar solid supports is additionally used. 

Ozonolysis of alkenes on solid supports, notably polyethylene <85JA5309>, has greatly increased the scope of the reaction in the preparation of 1,2,4-trioxolanes. Competing reactions of intermediates are avoided and the mild conditions often allow isolation of relatively unstable or previously unobtainable 1,2,4-trioxolanes. 

A solid-phase synthesis of furo[3,2-3]pyran derivatives utilizing highly functionalized sugar templates has been reported <2003JOC9406>. After incorporation of alkenes within the sugar template, such as compound 95, the solid support is introduced via formation of the acid amide. This immobilized system then allows a ruthenium-catalyzed ring-closing metathesis that leads to the formation of the fused oxacycles. 

The preparation of the silica supported a-fluorotropinone is easy to reproduce as a commercially available solid support was employed the asymmetric epoxidation has been applied to trans- and trisubstituted alkenes affording the corresponding... 

A study of the influence of the nature of the solid support showed that silica, celite, cellulose or magnesium sulphate in combination with borohydride can also be used successfully in the microwave-assisted reduction of carbonyl compounds. The choice of the solid support has been reported to influence the chemoselectivity of the reduction of chalcone. Under optimised conditions the reduction of the alkene can be suppressed using borohydride on silica, whereas the use of cellulose as solid support seems to favour C=C reduction (Scheme 4.11 )27. 

Trans -substituted diarylalkenes undergo oxidative cleavage upon treatment by potassium permanganate in the presence of moist alumina as a solid support (equation 32)158. Under the same conditions, cyclic alkenes, with medium-sized rings, give acyclic dialdehydes (equation 33). 

Dicobalt octacarbonyl, in Pauson—Khand reaction homogeneous catalysis, 11, 340 metal-coupled promoters, 11, 339 non-oxidative promoter-assisted, 11, 338 oxidative promoter-assisted, 11, 337 physical promoters, 11, 339 solid-supported promoters, 11, 339 Dicobalt triple-decker sandwiches, preparation, 3, 14 (+)-Dictamnol, via [5+2]-cycloadditions, 10, 613-614 Dicyclohexylborane, for alkene hydroboration, 9, 150... 

Several parameters of the hydrogenation affect the enantioselectivities and include temperature, hydrogen pressure, solvent, base, and catalyst.50 54 However, a significant increase of the S/C ratio, decrease of the hydrogen pressure from 2000 psig, and reduction in the cost of production of the alkene 37 are required for this technology to become economically feasible.50 Catalyst cost could also be reduced by use of solid supports that have the potential to improve TONs through catalyst recycle.55... 

Metallo-phthallocyanine (MePc) complexes are known as mild oxygenation catalysts for alkanes and alkenes and as functional models for enzymes, more in particular for monooxygenases like Cytochrome P450.[44] Among the many possible supports for such complexes, zeolite FAU topologies1451 are excellent materials for their encapsulation. [46 50] The low solubility of Me Pc complexes in general and their tendency to form adducts even in solution, giving rise to self-oxidation and subsequent self-destruction phenomena, make them the ideal candidates for their distribution as individual species on a solid support. 

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