Center of chirality

The stereochemical analysis of chiral structures starts with the identification of stereogenic units [101], Those units consist of an atom or a skeleton with distinct ligands. By permutation of the ligands, stcrcoisomcric structures arc obtained. The three basic stereogenic units arc a center of chirality (c.g., a chiral tctravalcnt... 

Chiral carbon atoms are common, but they are not the only possible centers of chirality. Other possible chiral tetravalent atoms are Si, Ge, Sn, N, S, and P, while potential trivalent chiral atoms, in which non-bonding electrons occupy the position of the fourth ligand, are N, P, As, Sb, S, Se, and Te. Furthermore, a center of chirality does not even have to be an atom, as shown in the structure represented in Figure 2-70b, where the center of chirality is at the center of the achiral skeleton of adamantane. 

In organic stereochemistry the terms center of chirality or center of asymmetry are often used usually they refer to an asymmetrically substituted C atom. These terms should be avoided since they are contradictions in themselves a chiral object by definition has no center (the only kind of center existing in symmetry is the inversion center). 

If X X = Y compounds of structure A have a center of chirality and the R-and S-enantiomers should be optically active. Since in Lewis add-base reactions exchange equilibria are often expected to be formed via transition state B, it seems quite difficult to synthesize one pure enantiomeric form ... 

The stereogenic centers of chiral dendrimers synthesized so far are either generated by asymmetric synthesis, or they are derived from molecules of the pool of chiral building blocks. The only investigation on chiral dendrimers, consisting of achiral building blocks exclusively, was published by Meijer et al., who synthesized dendrimers such as 31 [61] (Fig. 14). This compound ows its chiral-... 

For an adamantane-type compound, it is possible to substitute the four tertiary hydrogen atoms and make four quaternary carbon atoms. These carbon atoms can be asymmetric if the four substituents are chosen properly. It is possible to specify these chiral centers separately, but their chiralities can also be so interlinked that they collectively produce one pair of enantiomers with only one chiral center. Usually it is more convenient to collectively specify the chirality with reference to a center of chirality taken as the unoccupied centroid of the adamantane frame. 

An example of an iron-catalyzed C-C bond formation reaction was reported in 2001 [89]. Treatment of propargyl sulfides 87 with trimethylsilyldiazomethane in the presence of 5 mol% FeCl2(dppb) gave substituted homoallenylsilanes 88 in good to moderate yields (Scheme 3.43). The silanes 88d and 88e, which bear two centers of chirality, were obtained as 1 1 mixtures of diastereomers. Slight diastereoselectivity (2 1) was seen for the formation 88f, which is an axially chiral allene with a sterogenic center. 

So far, axially chiral donor-substituted allenes have rarely been used although they should be capable of transferring their stereochemical information to a new center of chirality. This lack may be due to the difficulties of generating axially chiral donor-substituted allenes with high enantiomeric purity. We expect that this gap will be filled in near future. 

The efficiency and convenience of the chiral allenylzinc reagents are demonstrated in the synthesis of subunits of several natural products. In a total synthesis of bafilomydn Vi, seven of the 13 stereogenic centers were introduced by means of allenylzinc chemistry [112]. Three centers of chirality in the C5-C11 fragment were constructed from the precursor (R)-mesylate and the (R)-aldehyde (Eq. 9.134). The TBS protecting group of the aldehyde is important for high diastereoselectivity. Four of the five stereogenic centers in the Cl 5-C25 subunit were likewise established (Eq. 9.135). 

During the past decade much attention was paid to the synthesis of chiral sulfinates with the sulfur atom as a sole center of chirality. A little earlier, Fava (105) had reported the asymmetric oxidation of methyl p-toluenesulfenate with (+)-monopercamphoric acid, yielding the corresponding sulfinate 65. The optical purity of the product was, however, very small (ca. 3%). 

However, the synthetic approaches to simple chiral thiosulfinates with sulfur as a sole center of chirality are relatively few in number, and for the most part their applicability is limited. 

The polarimetric method, in combination with the results of chemical correlation, made it possible to determine the optical purity of a range of chiral sulftnates (105-107), thiosulfinates (35,105), and sulfinamides (83) with the sulfur atom as a sole center of chirality. These compounds were converted by means of Grignard or alkyl-lithium reagents into sulfoxides of known specific rotations. This approach to the determination of optical purity of chiral sulfinyl compounds has at least two limitations. The first is that it cannot be applied to sterically hindered compounds [e.g., t-butyl /-butanethio-sulfinate 72 does not react with Grignard reagents]. Second, this... 

The addition of electrophilic reagents to chiral a,/3-unsaturated sulfoxides is also accompanied by asymmetric induction. Stirling and Abbott (318,322) found that the addition of bromine to the optically active (.R)-vinyl-p-tolyl sulfoxide 319 yields a mixture of diastereo-meric a,/3-dibromosulfoxides 320. Oxidation of this mixture gives the optically active sulfone 321, with a center of chirality at the a-carbon atom only. The optical purity (32%) of this sulfone was estimated by comparing its specific rotation with that obtained as a result of oxidation of diastereomerically pure sulfoxide (/ )-320. The assignment of configuration at the a-carbon atom was based on the analysis of the polarizabilities of substituents. 

Products containing as ligands PPh(l-Np)2 have two centers of chirality and two racemic diastereoisomers have been separated. The reaction of optically active PMePh 1 -Np leads to a racemic mixture since the phosphine is racemized under UV irradiation ... 

Clearly, upon using the enantiomeric catalyst [(S,S) instead of (R,R)] the opposite enantioselectivity of the overall process results. However, this effect is also seen with catalysts that are of analogous configuration, but not derived from trans-1,2-diaminocyclohexane (DACH). For example, the pseudo-ephedrine derived catalyst shown in Scheme 5, having (5)-configuration at the centers of chirality, shows some preference for the (5)-azlactone kinetically favors the (5)-azlactone in alcoholytic ring opening [37]. 

These chiral building blocks are incorporated into the target molecules in such a way that the configuration at the stereo centers remains unchanged. Since the relative configuration of newly produced centers of chirality can be controlled, virtually any enantiomerically pure product can be built around the chiral starting molecule. In the case of pheromones, chirality has a similar influence on their biological activity while one enantiomer attracts the insect species, the other may act as a repellent. ... 

CELLULOSE POLYSULFATASE CELLULOSE SYNTHASE CELSIUS TEMPERATURE CENNAMO PLOT ISO MECHANISMS Center of chirality,... 

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