Properties stereospecificity

In many cases only the racemic mixtures of a-amino acids can be obtained through chemical synthesis. Therefore, optical resolution (42) is indispensable to get the optically active L- or D-forms in the production of expensive or uncommon amino acids. The optical resolution of amino acids can be done in two general ways physical or chemical methods which apply the stereospecific properties of amino acids, and biological or enzymatic methods which are based on the characteristic behavior of amino acids in living cells in the presence of enzymes. 

Physical properties, which depend on molecular weight, the nature of the alkyl group, the nature of the initiator, stereospecificity, and crystallinity, range from viscous Hquids, through sticky Hquids and mbbery soHds, to brittie soHds. Polyethers with long alkyl side chains are waxy, however, as the alkyl group in such cases dominates physical properties. 

A complete mechanistic description of these reactions must explain not only their high degree of stereospecificity, but also why four-ir-electron systems undergo conrotatory reactions whereas six-Ji-electron systems undergo disrotatory reactions. Woodward and Hoifinann proposed that the stereochemistry of the reactions is controlled by the symmetry properties of the HOMO of the reacting system. The idea that the HOMO should control the course of the reaction is an example of frontier orbital theory, which holds that it is the electrons of highest energy, i.e., those in the HOMO, that are of prime importance. The symmetry characteristics of the occupied orbitals of 1,3-butadiene are shown in Fig. 11.1. 

A facile method for the stereospecific labeling of carbon atoms adjacent to an oxygenated position is the reductive opening of oxides. The stereospecificity of this reaction is due to virtually exclusive diaxial opening of steroidal oxides when treated with lithium aluminum hydride or deuteride. The resulting /ra/w-diaxial labeled alcohols are of high stereochemical and isotopic purity, with the latter property depending almost solely on the quality of the metal deuteride used. (For the preparation of m-labeled alcohols, see section V-D.)... 

Polymerizations catalyzed with coordination compounds are becoming more important for obtaining polymers with special properties (linear and stereospecific). The first linear polyethylene polymer was prepared from a mixture of triethylaluminum and titanium tetrachloride (Ziegler catalyst) in the early 1950s. Later, Natta synthesized a stereoregular polypropylene with a Ziegler-type catalyst. These catalyst combinations are now called Zieglar-Natta catalysts. 

Diels-Alder reaction and. 494-495 El reaction and, 392 E2 reaction and, 387-388 R.S configuration and, 297-300 S 1 reaction and, 374-375 S -2 reactions and, 363-364 Stereogenic center, 292 Stereoisomers, 111 kinds of, 310-311 number of, 302 properties of, 306 Stereospecilic, 228, 494 Stereospecific numbering, sn-glycerol 3-phosphate and, 1132 Steric hindrance, Sjvj2 reaction and, 365-366 Steric strain, 96... 

Of course, the trans isomer will give the opposite results the threo pair if the addition is syn and the erythro pair if it is anti. The threo and erythro isomers have different physical properties. In the special case where Y=W (as in the addition of Br2), the erythro pair is a meso compound. In addition to triple-bond compounds of the type ACsCA, syn addition results in a cis alkene and anti addition in a trans alkene. By the definition given on page 166 addition to triple bonds cannot be stereospecific, though it can be, and often is, stereoselective. 

As mentioned in Sect. 2.2, phosphine oxides are air-stable compounds, making their use in the field of asymmetric catalysis convenient. Moreover, they present electronic properties very different from the corresponding free phosphines and thus may be employed in different types of enantioselective reactions, m-Chloroperbenzoic acid (m-CPBA) has been showed to be a powerful reagent for the stereospecific oxidation of enantiomerically pure P-chirogenic phos-phine-boranes [98], affording R,R)-97 from Ad-BisP 6 (Scheme 18) [99]. The synthesis of R,R)-98 and (S,S)-99, which possess a f-Bu substituent, differs from the precedent in that deboranation precedes oxidation with hydrogen peroxide to yield the corresponding enantiomerically pure diphosphine oxides (Scheme 18) [99]. 

Some specific solutes diffuse down electrochemical gradients across membranes more rapidly than might be expected from their size, charge, or partition coefficients. This facilitated diffusion exhibits properties distinct from those of simple diffusion. The rate of facilitated diffusion, a uniport system, can be saturated ie, the number of sites involved in diffusion of the specific solutes appears finite. Many facihtated diffusion systems are stereospecific but, fike simple diffusion, require no metabolic energy. 

With increases in group size and social complexity, and the consequent expansion of diversity in communication, there is presumably selection pressure for unambiguous signals. Over time, evolutionary change may reduce unwanted complexity and act to refine specificity. Whether this results in reliance on the properties of a single component rather than those of the pattern provided by a complex mixture is conjectural. A reasonable expectation is that emitted semiochemical(s) can be reliably produced, and that their contents are acted upon by selection. The improvements in control which can thus be attained are seen in the operation of stereospecificity (Miiller-Schwarze et al, 1976). 

A particularly interesting property of the cycloamyloses is their ability to induce stereospecific precipitation. This was first recognized by Cramer and Dietsche (1959a) who were able to effect partial resolution of a series... 

The ring-opening of the cyclopropane nitrosourea 233 with silver trifiate followed by stereospecific [4 + 2] cycloaddition yields 234 [129]. (Scheme 93) Oxovanadium(V) compounds, VO(OR)X2, are revealed to be Lewis acids with one-electron oxidation capability. These properties permit versatile oxidative transformations of carbonyl and organosilicon compounds as exemplified by ring-opening oxygenation of cyclic ketones [130], dehydrogenative aroma-tization of 2-eyclohexen-l-ones [131], allylic oxidation of oc,/ -unsaturated carbonyl compounds [132], decarboxylative oxidation of a-amino acids [133], oxidative desilylation of silyl enol ethers [134], allylic silanes, and benzylic silanes [135]. 

The chemical properties of DPM have been probed with each of the procedures identified earlier. This carbene is known to react with alcohols to give ethers (Kirmse, 1963 Bethell et al., 1965), it adds to olefins non-stereospecifically to form cyclopropanes (Skell, 1959 Baron et al., 1973 Gaspar et al., 1980 Tomioka et al., 1984), and it is rapidly converted to a carbonyl oxide with oxygen (Werstiuk et al., 1984 Casal et al., 1984). 

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