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Stereospecific reduction

As a final example closing this chapter, the formation of difluoro olefins is discussed. As shown in Scheme 2.13.4, Motherwell, et al.,151 152 utilized phosphorus chemistry to effect the formation of these species in yields ranging from 55% to 65%. Furthermore, reduction stereospecifically converted these difluoro olefins to difluoromethylglycosides. In the last example, reduction was effected with thiophenol and allyltin induced the chain elongation to form a difluorobutenyl glycoside. [Pg.127]

In organic chemistry, LiH serves as a condensation agent. In the presence of trialkyl boranes very powerful reducing agents, LiBHR, which are soluble in THF, are obtained. These materials reduce aUphatic haUdes and in some cases highly stereospecific reductions can be accompHshed. [Pg.297]

Iron Sulfur Compounds. Many molecular compounds (18—20) are known in which iron is tetrahedraHy coordinated by a combination of thiolate and sulfide donors. Of the 10 or more stmcturaHy characterized classes of Fe—S compounds, the four shown in Figure 1 are known to occur in proteins. The mononuclear iron site REPLACE occurs in the one-iron bacterial electron-transfer protein mbredoxin. The [2Fe—2S] (10) and [4Fe—4S] (12) cubane stmctures are found in the 2-, 4-, and 8-iron ferredoxins, which are also electron-transfer proteins. The [3Fe—4S] voided cubane stmcture (11) has been found in some ferredoxins and in the inactive form of aconitase, the enzyme which catalyzes the stereospecific hydration—rehydration of citrate to isocitrate in the Krebs cycle. In addition, enzymes are known that contain either other types of iron sulfur clusters or iron sulfur clusters that include other metals. Examples include nitrogenase, which reduces N2 to NH at a MoFe Sg homocitrate cluster carbon monoxide dehydrogenase, which assembles acetyl-coenzyme A (acetyl-CoA) at a FeNiS site and hydrogenases, which catalyze the reversible reduction of protons to hydrogen gas. [Pg.442]

TiCl catalysts produced by the reduction of TiCl with Al(C2H 2d> subsequentiy treated first with an electron donor (diisoamyl ether), then with TiCl, are highly stereospecific and four to five times more active than d-TiCl (6). These catalysts were a significant advance over the earlier TiCl systems, because removal of atactic polymer was no longer required. They are often referred to as second-generation catalysts. The life of many older slurry process faciUties has been extended by using these catalysts to produce "clean" polymers with very low catalyst residues. [Pg.410]

In a first step, JS ocardia asteroides selectively oxidizes only (3)-pantolactone to ketopantolactone (19), whereas the (R)-pantolactone remains unaffected (47). The accumulated ketopantolactone is stereospecificaHy reduced to (R)-pantolactone in a second step with Candidaparapsilosis (product concentration 72 g/L, 90% molar yield and 100% ee) (48). Racemic pantolactone can also be converted to (R)-pantolactone by one single microbe, ie, Jiodococcus erythropolis by enantioselective oxidation to (3)-pantolactone and subsequent stereospecific reduction in 90% yield and 94% ee (product concentration 18 g/L) (40). [Pg.60]

An interesting feature of the synthesis is the use of allyl as a two-carbon extension unit. This has been used in the stereospecific synthesis of dicyclohexano-18-crown-6 (see Eq. 3.13) and by Cram for formation of an aldehyde unit (see Eq. 3.55). In the present case, mannitol bis-acetonide was converted into its allyl ether which was ozonized (reductive workup) to afford the bis-ethyleneoxy derivative. The latter two groups were tosylated and the derivative was allowed to react with its precursor to afford the chiral crown. The entire process is shown below in Eq. (3.59). [Pg.52]

Reduction of a 16a-bromo-17-ketone (but not the 16 -epimer) is a little less stereospecific than reduction of the 17-keto compound. When a 2a-bromo-3-keto steroid is reduced, at least 78 % of the 3/ -alcohol is obtained. [Pg.80]

Catalytic hydrogenation has been utilized extensively in steroid research, and the method has been found to be of great value for the selective and stereospecific reduction of various functional groups. A number of empirical correlations concerning selectivity and product stereochemistry compiled for steroid hydrogenations has been listed in a previous review. ... [Pg.111]


See other pages where Stereospecific reduction is mentioned: [Pg.310]    [Pg.11]    [Pg.103]    [Pg.265]    [Pg.230]    [Pg.240]    [Pg.240]    [Pg.247]    [Pg.247]    [Pg.353]    [Pg.308]    [Pg.251]    [Pg.310]    [Pg.11]    [Pg.103]    [Pg.265]    [Pg.230]    [Pg.240]    [Pg.240]    [Pg.247]    [Pg.247]    [Pg.353]    [Pg.308]    [Pg.251]    [Pg.278]    [Pg.42]    [Pg.537]    [Pg.234]    [Pg.277]    [Pg.277]    [Pg.309]    [Pg.310]    [Pg.157]    [Pg.15]    [Pg.283]    [Pg.259]    [Pg.71]    [Pg.81]    [Pg.81]    [Pg.83]    [Pg.84]    [Pg.90]    [Pg.156]    [Pg.319]    [Pg.394]    [Pg.47]    [Pg.7]    [Pg.182]   
See also in sourсe #XX -- [ Pg.60 ]

See also in sourсe #XX -- [ Pg.11 , Pg.98 ]




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Ketonucleosides stereospecific reduction

Oxidation-reduction reactions stereospecificity

Pyruvate stereospecific reduction

Stereospecific oxidation/reduction

Stereospecific reactions reductive

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