Chiral chiroptical properties

The stereogenic sulfur atom in sulfoxides is usually configurationally stable at room temperature thus, sulfoxides may be chiral based on this property alone1. In fact, there are many examples of optically active sulfoxides of both synthetic and natural origin. This chapter reviews the important methods for obtaining optically active sulfoxides, and discusses some reactions at sulfur which either leave the coordination number at three or increase it to four, generally with preservation of optical activity. It also describes briefly some recent studies on the conformational analysis and chiroptical properties of sulfoxides. 

Chiroptical Properties of Dendrimers with Chiral End Groups. .. 91... 

McGrath et al. have also thoroughly studied the chiroptical properties of dendrimers such as 40. They compared the optical activities of the series of 1st-, 2nd- and 3rd-generation compounds of type 40, considering the molar rotation per chiral unit ([ ]D/n) [75]. A big difference of the values was found between the generations which could possibly indicate chiral conformations inside the dendrimers, that enhance the optical rotation values per unit when... 

On the other hand, optically active telluroxides have not been isolated until recently, although it has been surmised that they are key intermediates in asymmetric synthesis.3,4 In 1997, optically active telluroxides 3, stabilized by bulky substituents toward racemization, were isolated for the first time by liquid chromatography on optically active columns.13,14 The stereochemistry was determined by comparing their chiroptical properties with those of chiral selenoxides with known absolute configurations. The stability of the chiral telluroxides toward racemization was found to be lower than that of the corresponding selenoxides, and the racemization mechanism that involved formation of the achiral hydrate by reaction of water was also clarified. Telluroxides 4 and 5, which were thermodynamically stabilized by nitrogen-tellurium interactions, were also optically resolved and their absolute configurations and stability were studied (Scheme 2).12,14... 

A distorted conjugated pair of double bonds is an intrinsically chiral chromophoric system, and its overall chiroptical properties depend on the reduced symmetry of the chromophore itself as well as on the perturbing action of a dissymmetric environment. 

An interesting series of s-trans planar dienes is that due to Walborsky and co-workers44,45. They prepared and studied the chiroptical properties of several compounds where the diene moiety is linked to a chirally substituted ring, such as 42 and 43. 

The carotenoid family have chiral centres which enable the use of circular dichroism. However, the chirality of carotenoids is not sufficiently characteristic so that the chiroptical properties do not serve as a good analytical tool. 

For general application of these chiral ligands, see (a) Kagan, H. B. Chiral Ligands for Asymmetric Catalysis in Morrison, J. D. ed. Asymmetric Synthesis, vol. 5, Chap. 1, Academic Press, New York, 1985. (b) Kagan, H. B., Sasaki, M. Optically Active Phosphines Preparation, Uses and Chiroptical Properties in Hartley, F. R. ed. The Chemistry of Organo Phosphorous Compounds, John Wiley Sons, New York, 1990, vol. 1, Chap. 3. 

In addition to 195-200, many other alkyl substituents and their derivatives have been introduced at position 9 of the fluorene nucleus in order to create a processible stable blue-emitting PF material, e.g., 203a-h [273-275,305], Chiral-substituted PFs 200 and 203g,h have been synthesized to study their chiroptical properties [306], particularly interesting due to polarized emission in such materials (see Chapter 5 in this book) (Chart 2.47). 

JJLM Comelissen, E Peeters, RAJ Janssen, and EW Meijer, Chiroptical properties of a chiral-substituted poly(thienylene vinylene), Acta Polym., 49 471-476, 1998. 

M Oda, HG Nothofer, U Scherf, V Sunjic, D Richter, W Regenstein, and D Neher, Chiroptical properties of chiral substituted polyfluorenes, Macromolecules, 35 6792-6798, 2002. 

Herrmann A, Ruettimann M, Thilgen C, Diederich F (1995) Multiple cyclopropanations of C70. Synthesis and characterization of bis-, tris-, and tetrakis-adducts and chiroptical properties of bis-adducts with chiral addends, including a recommendation for the configurational description of fullerene derivatives with a chiral addition pattern. Helv. Chim. Acta 78 1673-1704. 

Their isolation by flash chromatography on silica gel was comparatively easy. The CD spectra of related pairs of diastereomers whose addition pattern represent pairs of enantiomers, reveal pronounced Cotton effects and mirror image behavior. It is the chiral arrangement of the conjugated Jt-electron system within the fullerene core that predominantly determines the chiroptical properties. Adducts with a C2-... 

Laufersweiler MJ, Rohde JM, Chaumette J-L, Sarazin D, Parquette JR. Synthesis, aggregation, and chiroptical properties of chiral, amphiphilic dendrimers. J Org Chem 2001 66 6440-6452. 

Kiss, L. et al., Chiroptical properties and synthesis of enantiopure cis and trans pterocarpan skeleton. Chirality, 15, 558, 2003. 

Antus, S. et al., Chiroptical properties of 2,3-dihydrobenzo[6]furan and chromane chromophores in naturally occurring 0-heterocycles, Chirality, 13, 493, 2001. 

The inherent difficulty in analyzing enantiomers arises from the well-known fact that apart from their chiroptical characteristics, optical isomers have identical physical and chemical properties in an achiral environment (assuming ideal conditions). Therefore, methods of distinguishing enantiomers must rely on either their chiroptical properties (optical rotation, optical rotatory dispersion, circular dichroism), or must employ a chiral environment via diastereomer formation or interaction. Recently, it has become increasingly clear that such diastereomeric relationships may already exist in nonracemic mixtures of enantiomers via self-association in the absence of a chiral auxiliary (see Section 3.1.4.7.). 

Depending on whether enantiomers are distinguished 1) via a chiral auxiliary compound, or 2) characterized via their chiroptical properties, the following definitions110-12 are used (Section A.1.2.2.2.). 

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