Diol groups

The first practical method for asymmetric epoxidation of primary and secondary allylic alcohols was developed by K.B. Sharpless in 1980 (T. Katsuki, 1980 K.B. Sharpless, 1983 A, B, 1986 see also D. Hoppe, 1982). Tartaric esters, e.g., DET and DIPT" ( = diethyl and diisopropyl ( + )- or (— )-tartrates), are applied as chiral auxiliaries, titanium tetrakis(2-pro-panolate) as a catalyst and tert-butyl hydroperoxide (= TBHP, Bu OOH) as the oxidant. If the reaction mixture is kept absolutely dry, catalytic amounts of the dialkyl tartrate-titanium(IV) complex are suflicient, which largely facilitates work-up procedures (Y. Gao, 1987). Depending on the tartrate enantiomer used, either one of the 2,3-epoxy alcohols may be obtained with high enantioselectivity. The titanium probably binds to the diol grouping of one tartrate molecule and to the hydroxy groups of the bulky hydroperoxide and of the allylic alcohol... 

The C. 100-C. 101 diol group, protected as an acetonide, was stable to the Wit-tig reaction used to form the cis double bond at C.98-C.99, and to all the conditions used in the buildup of segment C.99-C. 115 to fully protected palytoxin carboxylic acid (Figure 1,1). 

The reaction depends, on the one hand, on the fact that fuchsin is decolorized by oxidizing agents (e.g. lead(IV) acetate) and, on the other hand, on the fact that lead(IV) acetate is reduced by compounds containing a-diol groups. It is, therefore, no longer available to decolorize the fuchsin. The fuchsin undergoes a Schiff reaction with the aldehydes that are formed [2]. 

Although lead tetraacetate can attack many polar and nonpolar functions in the steroid molecule, its greatest reactivity is towards vicinal diols. These diols are generally cleaved so rapidly under stoichiometric conditions that other alcohol functions in the molecule need not be protected. Thus lead tetraacetate in acetic acid at room temperature splits the 17a,20-diol group in (9) to yield the 17-ketone (10), the allylic A -3jS-alcohol remaining intact during this oxidation. Since lead tetraacetate is solublein many anhydrous... 

The vicinal diol groups of deoxy sugar phosphates can be cleaved by periodate in the usual conditions without affecting the stability of the phosphate group, so that this reaction can be used for preparative purposes in certain cases. Thus, if 3-deoxy glucose 6-phosphate (23) is... 

In theory, periodate oxidation could have given a clear-cut answer as to the composition of the isomeric mixture of deoxy ribose phosphates. The 4-phosphate (73), devoid of vicinal diol groups, should be resistant to periodate the 3-phosphate (74) should reduce one and only one molar equivalent of the oxidant and yield one molar equivalent of both formaldehyde and the phosphorylated dialdehyde (75), whereas the 5-phosphate (76) could be expected to reduce one molar equivalent of periodate relatively rapidly, followed by a slower overoxidation reaction owing to the oxidation of malonaldehyde, formed as a result of the glycol cleavage. 

In fact, it has been found (52) that in unbuffered solution, at room temperature, authentic 2-deoxy ribose 5-phosphate reduces more than 4 molar equivalents of periodate, but. that there is no noticeable slowing down of the reaction rate after the reduction of the first molar equivalent. This may be owing to the fact that only the aldehydo form (76) of 2-deoxy ribose 5-phosphate has a free vicinal diol group as the acyclic 2-deoxy ribitol 5-phosphate reduces one molar equivalent of periodate quite fast (58), it is probable that the time-curve of periodate uptake by the phosphorylated sugar reflects the rate of formation of the aldehyde form from the furanose form. 

In a similar way, 5-O-acetylthymidine was converted into the 3-deoxy-3-iodo derivative 72 in 55% yield. In this case, the replacement of the hydroxyl group by iodine was presumed to have taken place by retention of the configuration at C-3. The first intermediate in the reaction was proposed to be the phosphonate (70) which rapidly collapses to an O-3-cyclonucleoside (71) and the latter is subsequently attacked by iodide ion to give the product 72. It was also observed (106) that treatment of nucleosides containing a cis vicinal diol grouping such as 5-0-acetyluridine with triphenylphosphite methiodide failed to provide iodinated products but gave phosphonate derivatives instead. 

Cyclic diethylsilylene and di-tert.-butylsilylene derivatives have been used to protect diol groups in steroids and prostanoids [539-541]. N,0-bis(diethylhydrogensilyl)trifluoro-methylacetamide simultaneously converts Isolated hydroxyl groups to the diethyllu ogensilyl ether allowing a single step derivatization toVp used for the analysis of corticosteriods. 

This, and the tetraketone resulting from dehydration of the gem-diol groups, both explode under a hammer blow. 

The reaction product, with a dozen or more diol groups per silicone chain, is a viscous fluid exhibiting remarkable properties in surfactant chemistry. 

Another cis-diol (XV) derived from BP was obtained by the action of osmium tetroxide on 4,5-dihydroxybenzo[a]pyrene (86). The hydroxyl group at C5a is axial and that at C6 is equatorial, illustrating the relative rigidity of the BP ring system and the flexibility at C6 of the ring bearing the diol groups. 

Terminal Diol Group with Release of Formaldehyde... 

Sodium periodate also may affect tryptophan residues in some proteins. The oxidation of tryptophan can result in activity losses if the amino acid is an essential component of the active site. For instance, avidin and streptavidin may be severely inactivated by treatment with periodate, since tryptophan is important in forming the biotin-binding pocket. In addition, many other amino acid residues are susceptible to oxidation by periodate (Chapter 1, Section 1.1). Limiting the time of oxidation is important to restricting oxidation to diol groups while not affecting other protein structures. 

Figure 8.2 Crosslinkers containing a diol group in their cross-bridge design may be cleaved by oxidation with sodium periodate.

Microgels prepared in that way are hydrophilic, stable and do not tend to agglomerate. By oxidation of the diol group with sodium periodate a free aide-... 

Selective reaction at the ci.s-2,3-diol grouping of unprotected D-ribonucleosides has occasionally been observed. Treatment of D-ribonucleosides with tris(tetramethylammonium) trimetaphosphate in M sodium hydroxide for 4 days at room temperature led to a mixture of nucleoside 2 - and 3 -phosphates in yields of >70% no 5 -phosphate was detected.213 Reaction of ethyl (trichloromethyl)phos-phonate with nucleosides in N,N-dimethylformamide containing triethylamine, followed by basic hydrolysis of the reaction product, yielded 2 (3 )-phosphates in variable yields.214 The participation of the cis-diol grouping in the reaction was suggested by the failure of thymidine or 2, 3 -0-isopropylideneuridine to undergo reaction. 

Reports by Mattocks397,398 that 2-acetoxy-2-methylbutanoyl chloride reacts with 1,2- and 1,3-diols to afford chloroacetates led to an investigation into use of this type of reagent for selective transformation of the vicinal diol grouping in ribonucleosides. Greenberg and Mof-fatt399 chose to use 2-acetoxy-2-methylpropanoyl chloride (which lacks the complication of a chiral center), and, firstly, found that cis-... 

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