Structure chiral

If compounds have the same topology (constitution) but different topography (geometry), they are called stereoisomers. The configuration expresses the different positions of atoms around stereocenters, stereoaxes, and stereoplanes in 3D space, e.g., chiral structures (enantiomers, diastereomers, atropisomers, helicenes, etc.), or cisftrans (Z/E) configuration. If it is possible to interconvert stereoisomers by a rotation around a C-C single bond, they are called conformers. 

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... 

Separation of enantiomers by physical or chemical methods requires the use of a chiral material, reagent, or catalyst. Both natural materials, such as polysaccharides and proteins, and solids that have been synthetically modified to incorporate chiral structures have been developed for use in separation of enantiomers by HPLC. The use of a chiral stationary phase makes the interactions between the two enantiomers with the adsorbent nonidentical and thus establishes a different rate of elution through the column. The interactions typically include hydrogen bonding, dipolar interactions, and n-n interactions. These attractive interactions may be disturbed by steric repulsions, and frequently the basis of enantioselectivity is a better steric fit for one of the two enantiomers. ... 

Chiral Controller. (Synonymous with Chiral Auxiliary). A chiral structural unit which when attached to a substrate enhances stereoselectivity in the formation of new stereocenter(s). 

Hayashi et al. [18] have synthesized two diastereoisomers of 2,2 -bis[4-(alkyl)oxazol-2-yI]-l,T-binaphthyl,bis(oxazoline) derivatives possessing both binaphthyl axial chirality and carbon centered chirality (structures 9 and 10, Scheme 5). 

Fig. 17.5 Pi Hared chiral structure of Cu(pzc)2AgRe04 (a) and helical chain (b).

Symmetry breaking associated with chiral phenomena is a theme that recurs across the sciences—from the intricacies of the electroweak interaction and nuclear decay [1-3] to the environmentally influenced dimorphic chiral structures of microscopic planktonic foraminifera [4, 5], and the genetically controlled preferential coiling direction seen in the shells of snail populations [6, 7]. 

When the mesogenic compounds are chiral (or when chiral molecules are added as dopants) chiral mesophases can be produced, characterized by helical ordering of the constituent molecules in the mesophase. The chiral nematic phase is also called cholesteric, taken from its first observation in a cholesteryl derivative more than one century ago. These chiral structures have reduced symmetry, which can lead to a variety of interesting physical properties such as thermocromism, ferroelectricity, and so on. 

The isoborneol-10-sulfonamide unit represents a new type of chiral structure that has been successfully used in different reactions of organometallic addition to aldehydes with excellent results in some cases. In particular, this unique type of ligand has been investigated by Yus and Ramon for the enantioselective... 

The requirement for the existence of enantiomers is a chiral structure. Chirality is solely a symmetry property a rigid object is chiral if it is not superposable by pure rotation or translation on its image formed by inversion. Such an object contains no rotoinversion axis (or rotoreflection axis cf. Section 3.1). Since the reflection plane and the inversion center are special cases of rotoinversion axes (2 and 1), they are excluded. 

Molecules with a planar coordination figure do not contain planar atoms . Further, tetrahedral atoms , chiral atoms etc. are nonsense. A minimum of four atoms is required for a chiral structure. 

Figure 84 Chiral structures—the first examples of transition-metal-based discrete supramolecular assemblies with controlled stereochemistry.

It should be possible to use the special properties of chiral structures for particular separation problems. According to Belinski and Tencer, one possible way in which nature solved the ribose problem could have involved an enantioselective and diastereoselective purification process acting on a mixture of biomolecules, which left ribose as the only molecule available for further reactions. The authors propose a theoretical mechanism in which a type of chromatographic process occurs at chiral mineral surfaces. This paper is likely to stimulate new experiments as well as the quest for as yet unknown surfaces which can separate racemic carbohydrate mixtures. The question arises, however, as to whether there were minerals present on the young Earth which are now unknown, as they no longer exist on the Earth of today (Belinski and Tencer, 2007). 

Figure 4.35 shows the CD and UV spectra for 48 in isooctane. The observation of the Cotton effect indicates that the chromophore in the polymer, which is a main-chain segment over which the silicon a and o orbitals are electronically delocalized, exists in a chiral structure a helix. 

Although biaryl-based chiral molecules are the most extensively studied, also other molecular frameworks are associated to high twisting powers and thus suitable for stereochemical studies. One of the first chiral structures used in... 

Many efforts have been made to develop salen catalysts for the epoxidation of unfunctionalized olefins, and such work has been well documented.93 Very recently, Ito and Katsuki94 proposed that the ligand of the oxo salen species is not planar, but folded as shown in Figure 4-7 (R/ / H, R2 = H, L = achiral axial ligand). This folded chiral structure amplifies asymmetric induction by the Mn-salen complex. This transition state proposed by Ito and Katsuki is not compatible with the proposal by Palucki et al.95 that the salen ligands of oxo species are planar. 

DPIBF, the resulting 119 was optically active. This suggests that the progenitor of 119 has the allene structure 117 rather than other conceivable constitutions [80, 81]. Even early quantum-chemical calculations on 117 showed a strongly bent, chiral structure, although the enantiomerization barrier was not correctly estimated [19]. 

Finally, reference must be made to the important and interesting chiral crystal structures. There are two classes of symmetry elements those, such as inversion centers and mirror planes, that can interrelate. enantiomeric chiral molecules, and those, like rotation axes, that cannot. If the space group of the crystal is one that has only symmetry elements of the latter type, then the structure is a chiral one and all the constituent molecules are homochiral the dissymmetry of the molecules may be difficult to detect but, in principle, it is present. In general, if one enantiomer of a chiral compound is crystallized, it must form a chiral structure. A racemic mixture may crystallize as a racemic compound, or it may spontaneously resolve to give separate crystals of each enantiomer. The chemical consequences of an achiral substance crystallizing in a homochiral molecular assembly are perhaps the most intriguing of the stereochemical aspects of solid-state chemistry. 

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