Stereoisomerism configurational

A method for designating the stereoisomeric configuration of a chiral carbon atom within a molecular entity. The designation d was arbitrarily assigned to (-F)-glycer-aldehyde, and (-)-glyceraldehyde was assigned the label... 

The introduction of four alkyl groups, bulkier than ethyl, at the lower rim of calix[4]arenes locks the macrocycle in one of the four possible stereoisomeric configurations cone, partial cone, 1,3-altemate, 1,2-alternate (Fig. 7.2). 

The possibility for different spatial arrangements of atoms or groups in molecules gives rise to the phenomenon of stereoisomerism. There are two forms of stereoisomerism, configurational and conformational. 

Organic phosphorus compounds, primarily inositolhexaphosphates (probably more than 50% of all organic phosphates), occiu in soils. The parent cyclic polyol, inositol, exists in numerous stereoisomeric configurations, of which myo-, scyllo-, neo-, and cZZ-inositol have been isolated from soils as phosphate esters. The hexaphosphate of myoinositol (myo-IHP), phytic acid, occurs in plant tissues. It often occurs as phytin, the calcium magnesium salt. Esters of myo-IHP are readily adsorbed in acidic soil solution by clay minerals and finely divided hydrated oxides of iron and aluminum. Organic sulfur compounds present in soils probably occur primarily as amino acids—e.g., cysteine, cystine, and methionine. 

Inositol phosphates are often the most abundant organic phosphorus compounds in soils, although they are less common in aquatic samples. They include a sequence of phosphate monoesters, from inositol hexa-kisphosphate to inositol monophosphate (Mandal and Islam, 1979 Harrison, 1987), in various stereoisomeric configurations [myo, scyllo, neo, B-cbiro) of the sugar inositol (Anderson and Malcolm, 1974 Anderson et al., 1974 Cosgrove, 1980 Harrison, 1987 Turner et al, 2002). These compounds are... 

On the other hand if attachment of successive monomer units takes place at carbon 4 through a radical of the form II then this is referred to as 1,4-addition. In this case, however, two stereoisomeric configurations known as cis and trans are possible... 

Configurational Stereoisomerism Configurational isomers are stereoisomers that do not readily interconvert under normal conditions and thus can be separated and isolated. Interconversion in these stereoisomers usually... 

Isomeric alkenes may be either constitutional isomers or stereoisomers There is a sizable barrier to rotation about a carbon-carbon double bond which corresponds to the energy required to break the rr component of the double bond Stereoisomeric alkenes are configurationally stable under normal conditions The configurations of stereoisomeric alkenes are described according to two notational systems One system adds the prefix CIS to the name of the alkene when similar substituents are on the same side of the double bond and the prefix trans when they are on opposite sides The other ranks substituents according to a system of rules based on atomic number The prefix Z is used for alkenes that have higher ranked substituents on the same side of the double bond the prefix E is used when higher ranked substituents are on opposite sides... 

Eleven chirality centers may seem like a lot but it is nowhere close to a world record It is a modest number when compared with the more than 100 chirality centers typ ical for most small proteins and the thousands of chirality centers present m nucleic acids A molecule that contains both chirality centers and double bonds has additional opportunities for stereoisomerism For example the configuration of the chirality center m 3 penten 2 ol may be either R or S and the double bond may be either E or Z There fore 3 penten 2 ol has four stereoisomers even though it has only one chirality center... 

The task of relating carbohydrate configurations to names requires either a world class memory or an easily recalled mnemonic A mnemonic that serves us well here was pop ularized by the husband-wife team of Lours F Fieser and Mary Fieser of Harvard Uni versity m their 1956 textbook Organic Chemistry As with many mnemonics it s not clear who actually invented it and references to this particular one appeared m the chem ical education literature before publication of the Fiesers text The mnemonic has two features (1) a system for setting down all the stereoisomeric d aldohexoses m a logical order and (2) a way to assign the correct name to each one... 

Both maltose and cellobiose have a free anomeric hydroxyl group that is not involved in a glycoside bond The configuration at the free anomeric center is variable and may be either a or (3 Indeed two stereoisomeric forms of maltose have been iso lated one has its anomeric hydroxyl group m an equatorial orientation the other has an axial anomeric hydroxyl... 

Configurations around any double bond give rise to cis and trans stereoisomerism. 

In addition to constitution and configuration, there is a third important level of structure, that of conformation. Conformations are discrete molecular arrangements that differ in spatial arrangement as a result of facile rotations about single bonds. Usually, conformers are in thermal equilibrium and cannot be separated. The subject of conformational interconversion will be discussed in detail in Chapter 3. A special case of stereoisomerism arises when rotation about single bonds is sufficiently restricted by steric or other factors that- the different conformations can be separated. The term atropisomer is applied to stereoisomers that result fk m restricted bond rotation. ... 

Diastereomers include all stereoisomers that are not related as an object and its mirror image. Consider the four structures in Fig. 2.3. These structures represent fee four stereoisomers of 2,3,4-trihydroxybutanal. The configurations of C-2 and C-3 are indicated. Each stereogenic center is designated J or 5 by application of the sequence rule. Each of the four structures is stereoisomeric wife respect to any of fee others. The 2R R and 25,35 isomers are enantiomeric, as are fee 2R, iS and 25,3J pair. The 21 ,35 isomer is diastereomeric wife fee 25,35 and 2R,3R isomers because they are stereoisomers but not enantiomers. Any given structure can have only one enantiomer. All other stereoisomers of feat molecule are diastereomeric. The relative configuration of diastereomeric molecules is fiequently specified using fee terms syn and anti. The molecules are represented as extended chains. Diastereomers wife substituents on the same side of the extended chain are syn stereoisomers, whereas those wife substituents on opposite sides are anti stereoisomers. 

In such a process, the water molecule fonned in the elimination step is captured primarily fiom the fixmt side, leading to net retention of configuration for the alcohol. For the ester, the extent of retention and inversion is more balanced, although it vari among individual systems. It is clear om die data in Table 5.18 that the two pairs of stereoisomeric amines do not form the same intermediate, even though a simple mechanistic interpretation would sugg that both would fmm the 2-decalyl cation. The coUap of the ions to product is pvidoitly so rapid that diere is not time for relaxation of the initially formed intermediates to reach a common stnicture. 

A study of the lithium-ammonia reduction of 14-en-16-ones would extend our understanding of the configuration favored at C-14 in metal-ammonia reductions. Although several simple 14-en-16-ones are known, their reduction by lithium and ammonia apparently has not been described in the literature. Lithium-ammonia reduction of A-nortestosterone, a compound that structurally is somewhat analogous to a 14-en-16-one, affords roughly equal amounts of the 5a- and 5 -dihydro-A-nortestosterones. " This finding was interpreted as indicating that there is little difference in thermodynamic stability between the two stereoisomeric products. 

The two stereoisomeric furanose forms of D-erythrose ae naned a-D-erythro-furanose and p-D-erythrofuranose. The prefixes a and p describe the relative configuration of the anorneric cabon. The configuration of the anorneric cabon is cornpaed with that of the highest numbered chirality center in the molecule—the one that determines whether the cabohydrate is d or l. Chemists use a simplified, informal version of the lUPAC rules for assigning a and p that holds for ca bohydrates up to and including hexoses. 

The preparation of a pair of stereoisomeric enamines to which configurations were assigned has been reported 125). When the mesitoate esters 171 and 172... 

The palladium-catalyzed cyclization of compound 138 amply demonstrates the utility of the Stille reaction as a macrocyclization method (see Scheme 37). This efficient ring closure is just one of many examples disclosed by J.E. Baldwin and his group at Oxford.58 Interestingly, compound 138 can be employed as a stereoisomeric mixture of vinylstannanes because both stereoisomers converge on the same cyclized product. To rationalize this result, it was suggested that the configuration of the vinylstannane moiety is conserved in the cyclization, but that the macrocycle resulting from the (Z)-vinylstannane stereoisomer isomerizes to the thermodynamically favored trans product under the reaction condi-... 

Finally, since besides the inductive effect of the sulfoxide and the sulfone functional groups, hydrogen bonding, field effects and steric effects to solvation may or may not work in the same direction, the pKx values can be useful in assigning configurations of suitable pairs of stereoisomeric sulfoxide and sulfone carboxylic acids291. 

A good nucleophile, as is the case for most primary or secondary amines, can react through the two above mechanisms, either in the absence or presence of Ag20, affording the pertinent stereoisomeric substitution derivative. From a practical point of view, the presence of Ag20 represents the best choice, since it grants faster reactions and full retention of configuration. 

In the previous chapters, we discussed electron distrihution in organic molecules. In this chapter, we discuss the three-dimensional stracture of organic compounds. The structure may be such that stereoisomerism is possible. Stereoisomers are compounds made up of the same atoms bonded by the same sequence of bonds but having different three-dimensional stracmres which are not interchangeable. These three-dimensional structures are called configurations. 

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