Thioacetals, reduction

The hydroxyl group of (+)-32 was protected as a methoxymethyl ether to give ether (+)-63 in 80% yield (Scheme 12). To reduce the carbonyl group of (+)-63 to a methylene moiety of (+)-66 (Scheme 13), we tried the thioacetal reduction method. However, the attempt was unsuccessful because of the exchange of the acetal group at the 1-position by a thioacetal group. Although we also tried the... 

NiCl2 (1 eq) + NaBH4 (2 eq) Ni-boride + thioacetal reduction product... 

The synthesis of 11-oxaprostaglandlns from o-glucose uses the typical reactions of gl cofuranose diacetonide outlined on p. 267. Reduction of the hemiacetal group is achieved a thioacetal. The carbon chains are introduced by Wittig reactions on the aldehyde grou] which are liberated by periodate oxidation and laaone reduction (S. Hanessian, 1979 G Lourens, 1975). 

Thioacetyl derivatives (155) are obtained by direct heterocyclization reactions (365. 378, 563) and by a sulfur-oxygen exchange" reaction involving thioacetic acid and A-2-oxazoline-5-one (154) or A-2-thiazoline-5-one (156) (Scheme 81) (365, 378, 379). Ra-Ni reduction of 155 affords the 5-unsubstituted thiazole (379). 

Chrzanowska and Rozwadowska (60) performed a total synthesis of ( )-43, using amine 49 and the thioacetal of methoxycarbonylpiperonal (26) as substrates (Scheme 13). These two synthons were joined together under the influence of LDA, and the resulting addition product 50 was subjected to reductive desulfurization with Raney nickel to give racemic peshawarine (43). 

The "smelly shoe" of the elements. The oxidation product S02 has an acrid, burning smell, the reduction product H2S stinks like rotten eggs and is very toxic. Sulfur is, nevertheless, a most useful element. It occurs in elemental form and has therefore been known for a long time is mentioned in the Old Testament. Its main application today is in the production of fertilizers. Considerable amounts of sulfur are used in tire production for vulcanization. Sulfur is also a component of gunpowder. Physiologically indispensable as thioacetic acid and especially the S-S bridges that fix proteins in their shapes (e.g. insulin, but also in perms). A 70-kg human being contains 140 g of sulfur. 

An unusual reductive elimination can ensue from titanacyclobutanes possessing an alkenyl group at the carbon a to the titanium atom. Thus, alkenylcarbene complexes 48, prepared by the desulfurization of (fy-unsaturated thioacetals 49 or l,3-bis(phe-nylthio)propene derivatives 50 with a titanocene(II) reagent, react with terminal olefins to produce alkenylcyclopropanes 51 (Scheme 14.22, Table 14.4) [37]. This facile reductive... 

A somewhat similar configurational correlation between (leva)-glyceraldehyde and (dexfro)-lactic acid has been made by Wolfrom, Lemieux, Olin and Weisblat.36 Reductive desulfurization of tetra-acetyl-2-methyl-D-glucose diethyl thioacetal (XXVII) and hydrolysis of the product gave 2-methyl-l-desoxy-D-glucitol (XXVIII) oxidation... 

In- the preceding section the reductive desulfurization of some substances which are both thioglycosides and thioacetals has been mentioned here the hydrogenolysis of the simple 1-thioglycosides will be discussed. 

The reduction of a-carbonyl diphenyldi-thioacetals [212] was reported to be self-catalyzed (with formation in the course of the cathode process of the couple... 

Scheme 48 Hemithioacetals and thioacetals via reduction of disulfides in the presence of ketone.

Mesylation of alcohol 14 and hydrolysis of the acetal with oxalic acid leads to the key decalone 16 which cyclises in the presence of NaH in dioxane to afford twistanone 17 in quantitative yields. The elimination of the carbonyl group was carried out by an alternative method to the Wolff-Kishner reduction, which involves the thioacetalisation of the twistanone (18) with ethane-1,2-dithiol and removal of the resulting thioacetal by Raney nickel in boiling ethanol (62% yield). 

Because carbohydrates are so frequently used as substrates in kinetic studies of enzymes and metabolic pathways, we refer the reader to the following topics in Ro-byt s excellent account of chemical reactions used to modify carbohydrates formation of carbohydrate esters, pp. 77-81 sulfonic acid esters, pp. 81-83 ethers [methyl, p. 83 trityl, pp. 83-84 benzyl, pp. 84-85 trialkyl silyl, p. 85] acetals and ketals, pp. 85-92 modifications at C-1 [reduction of aldehydes and ketones, pp. 92-93 reduction of thioacetals, p. 93 oxidation, pp. 93-94 chain elongation, pp. 94-98 chain length reduction, pp. 98-99 substitution at the reducing carbon atom, pp. 99-103 formation of gycosides, pp. 103-105 formation of glycosidic linkages between monosaccharide residues, 105-108] modifications at C-2, pp. 108-113 modifications at C-3, pp. 113-120 modifications at C-4, pp. 121-124 modifications at C-5, pp. 125-128 modifications at C-6 in hexopy-ranoses, pp. 128-134. 

To facilitate accesses to suitably functionalized sialic acid derivatives and complex sialyloligosaccharides for other usehil neoglycoconjugates, phase transfer catalysis (PTC) has been exploited extensively [for reviews see 42]. This process provided a wide range of carbohydrate derivatives under essentially clean Sn2 transformations. In the case of acetochloroneuraminic acid 1, the PTC reactions always provided inverted a-sialic acid derivatives [43]. para-Formylphenyl sialoside 7 [44], together with many other sialoside derivatives such as 8-10 [43], including thioacetate 12 [45] and azide 14 [46], were thus obtained (Scheme 1). Aldehyde 7 and similar glycosides are of particular interest since they could be directly conjugated to protein by reductive amina-tion after suitable deprotection [44]. 

To further exploit the potential usefiilness of this new family of clusters, monoadduct 54 was saponified into 55 (0.05 M NaOH, quant) and condensed to L-lysine methyl ester using 2-ethoxy-l-ethoxycarbonyl-l,2-dihydroquinoline (EEDQ) to give extended dimer 56 in 50 % yield together with monoadduct in 15 % yield [75]. Additionally, tert-butyl thioethers 52 could be transformed into thiols by a two step process involving 2-nitrobenzenesulfenyl chloride (2-N02-PhSCl, HOAc, r.t, 3h, 84%) followed by disulfide reduction with 2-mercaptoethanol (60%). Curiously, attempts to directly obtain these thiolated telomers by reaction with thioacetic acid f ed. These telomers were slightly better ligands then lactose in inhibition of binding of peanut lectin to a polymeric lactoside [76]. 

In the only report of the generation of a pyridazino[3,4- ][l,4]thiazine <1992JHC1409>, reduction of a 2-(3-nitropyridazin-4-yl)thioacetic acid derivative is accompanied by cyclization (Equation 164). 

Reductive desulfenylation of the thioacetal 2 should produce 4 a and 4 b in nearly equal amounts. Subsequent silylation of 4, generated in this manner, gave 5a and 5 b with the same diastereomeric ratio as before. Only when the desulfenylation of 2 was performed in the presence of chlorotrimethylsilane, were the diastereomers of 5 obtained in a different ratio (5 a, d.r. 60 40). This demonstrates that the silylation reaction of 4 is faster in this case than the epimerization. 

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