Stereoisomers defined

The ligand tetracarboxyethyl DOTA derivative (TCE-DOTA) was synthesized as a mixture of the six stereoisomers defined by the absolute configuration of the four chiral carbons, RRRR/SSSS pair, RSSS/SRRR pair, RSRS and RRSS, which were separated, crystallized and their crystal structures determined [78,79]. The crystal structures of the Eu3+, Gd3+ and Tb3+ complexes of the TCE-DOTA... 

The earlier sections have only considered the way atoms are bonded to each other in a molecule (topology) and how this is translated into a computer-readable form. Chemists define this arrangement of the bonds as the constitution of a molecule. The example in Figure 2-39, Section 2.5.2.1, shows that molecules with a given empirical formula, e.g., C H O, can have several different structures, which are called isomers [lOOj. Isomeric structures can be divided into constitutional isomers and stereoisomers (see Figure 2-67). 

The aldotetroses are the four stereoisomers of 2 3 4 trihydroxybutanal Fischer pro jections are constructed by orienting the molecule m an eclipsed conformation with the aldehyde group at the top The four carbon atoms define the mam chain of the Fischer projection and are arranged vertically Horizontal bonds are directed outward vertical bonds back... 

Unsaturated -lactone 34 adopts a well-defined conformation and provides a suitable platform for the introduction of the stereogenic center at C-24 (monensin numbering). Catalytic hydrogenation of the carbon-carbon double bond in 34 takes place preferentially from the less hindered side of the molecule and provides an 8 1 mixture of stereoisomers in favor of 35 (100% yield). Cleavage of -lactone 35 with concentrated hydriodic acid at 130°C, followed by treatment of the resultant iodide 36 with triphenylphosphine, completes the synthesis of intermediate 19. 

Now that the allylic oxidation problem has been solved adequately, the next task includes the introduction of the epoxide at C-l and C-2. When a solution of 31 and pyridinium para-tolu-enesulfonate in chlorobenzene is heated to 135°C, the anomeric methoxy group at C-l 1 is eliminated to give intermediate 9 in 80% yield. After some careful experimentation, it was found that epoxy ketone 7 forms smoothly when enone 9 is treated with triphenyl-methyl hydroperoxide and benzyltrimethylammonium isopropoxide (see Scheme 4). In this reaction, the bulky oxidant adds across the more accessible convex face of the carbon framework defined by rings A, E, and F, and leads to the formation of 7 as the only stereoisomer in a yield of 72%. 

When the related saccharin derived sultam (R)-29 is converted into the (Z)-boron enolate and subsequently treated with aldehydes,. vy -diastereomers 30 result almost exclusively. Thus, the diasteromeric ratios, defined as the ratio of the major product to the sum of all other stereoisomers, surpass 99 1. Hydroperoxide assisted saponification followed by esterification provides carboxylic esters 31 with recovery of sultam 32106a. 

Stereoselectivity, in particular, enantioselectivity, is the most important feature of enzymes. It should be stressed that enzymes are capable of recognizing any type of chirality of the substrates. It does not seem necessary to prove here how important the synthesis of sterically defined products is, because the differences in biological activity of particular stereoisomers of a given substance are well known. There are three approaches to the synthesis of enantiomerically enriched... 

Percentage cross-reactivity is defined as the ratio of the IC50 of the testing substance (ractopamine stereoisomer or metabohte) and the IC50 of the ractopamine racemic mixture, expressed as a percentage. 

A stereocenter is defined as an atom bearing groups of such nature that an interchange of any two groups will produce a stereoisomer. 

However, soon afterward the original authors [137] as well as one other group, simultaneously revised the structures of punaglandins 3 (97) and 4 (98) based on synthesis of all possible stereoisomers [138]. These synthetic efforts not only established that the stereochemistry at Cl2 was opposite to that proposed, they also defined the complete absolute stereochemistry in punaglan-... 

Even this brief list may suffice to show that it would be a formidable task to develop a system of factorization free of avoidable redundancies, and that such a system would not be satisfactory even if it avoids arbitrary choices. It would require a rule disqualifying certain centers or lines of stereoisomerism on the basis of their relationships to other potential elements in the same molecule. Such definitions would not be self-contained. Moreover, the products of factorization that would take the place of those dropped cannot be limited to points or lines that are merely differently defined. There would have to be a virtually open-ended proliferation of new elements. This highly undesirable feature would not be offset by a major benefit of the revised system such as a correlation between the numbers of elements and of stereoisomers, because a complete elimination of all redundancies does not seem possible. We conclude that the system of choice is the one based on the principle that the elements of stereoisomerism allow no further factoring. Accordingly we think it best to retain the definitions given in Sects. IV and VI and their strictures that all centers and lines be occupied by atoms or bonds. 

In the tetra-bridged phosphocavitands, the preorganized structure is imposed by the fixed boat-chair conformation of the four fused eight-mem-bered rings. Inwards (i) and outwards (o) configurations are defined relatively to the endo and exo orientations of the P=X bonds (X=0, S, electron pair), and six different stereoisomers arise from the equatorial or axial orientation of the substituents on the phosphorus atoms (Scheme 3). 

Now, you may have noticed that the hydroxyl group in methylecgonine is oriented differently from that in tropine. In methylecgonine it is easy to define the position of the hydroxyl, since this is a chiral centre and we can use the R/S nomenclature. An alternative stereoisomer of tropine exists, and this is called pseudotropine. How can we define the configuration for the hydroxyl when the plane of symmetry of the molecule goes through this centre and means this centre is not chiral but can exist in two different arrangements ... 

Note that the pro-R and pro-S hydrogens in L-malate can be readily discerned by mentally replacing either hydrogen by a deuterium atom and then applying the RS or Cahn-Ingold-Pre-log system for defining R and S stereoisomers. 

The butadiene polymers represent another cornerstone of macromolecular stereochemistry. Butadiene gives rise to four different types of stereoregular polymers two with 1,2 linkage and two with 1,4. The first two, isotactic (62) and syndiotactic (25), conform to the definitions given for vinyl polymers, while the latter have, for eveiy monomer unit, a disubstituted double bond that can exist in the two different, cis and trans, configurations (these terms are defined with reference to the polymer chain). If the monomer units all have the same cis or trans configuration the polymers are called cis- or trans-tactic (30 and 31). The first examples of these stereoisomers were cited in the patent literature as early as 1955-1956 (63). Structural and mechanistic studies in the field have been made by Natta, Porri, Corradini, and associates (65-68). 

One way to gain fast access to complex stmctures are multicomponent reactions (MCRs), of which especially the isocyanide-based MCRs are suitable to introduce peptidic elements, as the isonitrile usually ends up as an amide after the reaction is complete. Here the Ugi-4 component reaction (Ugi CR) is the most suitable one as it introduces two amide bonds to form an M-alkylated dipeptide usually (Fig. 2). The Passerini-3CR produces a typical element of depsipeptides with ester and amide in succession, and the Staudinger-3CR results in p-lactams. The biggest unsolved problem in all these MCRs is, however, that it is stUl close to impossible to obtain products with defined stereochemistry. On the other hand, this resistance, particularly of the Ugi-reaction, to render diastereo- and enantioselective processes allows the easy and unbiased synthesis of libraries with all stereoisomers present, usually in close to equal amounts. 

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