Chiral compounds stereoselectivity

M. R. Kula, U. Kragl, Dehydrogenases in the synthesis of chiral compounds" in R. Patel, Stereoselective Biocatalysis, Marcel Dekker, 2000, 839. 

The one chiral centre in (30) is used to set up four other chiral centres stereoselectIvely. Draw out the synthesis, giving the correct stereochemistry for all compounds. 

Amino alcohols, which have a broad spectrum of biological activities, can be categorized as adrenahne-like with one chiral center at C-1 or as ephedrine-like with two chiral centers at C-1 and C-2 (Scheme 7). Although a variety of methods have been developed for the stereoselective preparation of 1,2-amino alcohols, " in most cases it is easier and more efficient to prepare these important compounds stereoselectively starting from chiral cyanohydrins (Scheme... 

Stereoselectivity, the production of one enantiomer of a chiral compound (chiral products are marked with an asterisk in Figure 1.1)... 

Crown-ether CSPs have the ability to include some chiral molecules stereoselectively. These CSPs are well suited for the separation of amino acids and compounds containing a primary amine at or near the stere-ogenic centre. The most used commercially available crown-ether CSP is Crownpak CR (-I-), developed by Daicel (Osaka, Japan). 

One might anticipate that there would be a rate difference for the reaction of enantiomers with a chiral compound. The first demonstration of stereoselectivity in an outer-sphere electron transfer was as recent as 1980. Since then such asymmetric induction has been established with a number of examples, nearly all involving outer-sphere redox reactions. Thus, consider the two reactions... 

With the increasing demand for chiral nonracemic compounds, stereoselective methods for the synthesis of 1,3-oxazine derivatives and applications of enantiopure 1,3-oxazines in asymmetric transformations have gained in importance in the past decade, as reflected by the increasing trend in the number of publications on this topic, and accordingly by the share of this topic in the present compilation. The limited size of this survey and the scope of this chapter do not allow a discussion here of the applications of 1,3-oxazines in polymer chemistry and the synthesis and properties of 1,3-benzoxazine-containing hetero-calixarenes. 

Additive-Induced Stereoselectivity Stereoselectivity in a reaction between achiral reactants is additive induced when (a) stereogenic unit(s) is (are) stereoselectively generated under the influence of a noncovalently bound chiral compound (e.g., solvent, catalyst). 

Introduction of the allene structure into cycloalkanes such as in 1,2-cyclononadiene (727) provides another approach to chiral cycloalkenes of sufficient enantiomeric stability. Although 127 has to be classified as an axial chiral compound like other C2-allenes it is included in this survey because of its obvious relation to ( )-cyclooctene as also can be seen from chemical correlations vide infra). Racemic 127 was resolved either through diastereomeric platinum complexes 143) or by ring enlargement via the dibromocarbene adduct 128 of optically active (J3)-cyclooctene (see 4.2) with methyllithium 143) — a method already used for the preparation of racemic 127. The first method afforded a product of 44 % enantiomeric purity whereas 127 obtained from ( )-cyclooctene had a rotation [a]D of 170-175°. The chirality of 127 was established by correlation with (+)(S)-( )-cyclooctene which in a stereoselective reaction with dibromocarbene afforded (—)-dibromo-trans-bicyclo[6.1 0]nonane 128) 144). Its absolute stereochemistry was determined by the Thyvoet-method as (1R, 87 ) and served as a key intermediate for the correlation with 727 ring expansion induced... 

Nickel and other transition metal catalysts, when modified with a chiral compound such as (R,R)-tartaric acid 5S), become enantioselective. All attempts to modify solid surfaces with optically active substances have so far resulted in catalysts of only low stereoselectivity. This is due to the fact that too many active centers of different structures are present on the surface of the catalysts. Consequently, in asymmetric hydrogenations the technique of homogeneous catalysis is superior to heterogeneous catalysis56). However, some carbonyl compounds have been hydrogenated in the presence of tartaric-acid-supported nickel catalysts in up to 92% optical purity55 . 

As can be seen from Figure 2, the (/ )-enantiomers (eutomers) of the silanols 3 and 7 show a significantly higher affinity for muscarinic M2 and M3 receptors than the corresponding (S)-antipodes (distomers). To the best of our knowledge, this is the first example of a biological discrimination between enantiomeric silicon compounds, with the silicon atom as the center of chirality. The stereoselectivity indices SI [SI = Kn S)/Kd(R) for sila-procyclidine (3) are 1.8 (M2) and 4.1 (M3), respectively. For sila-tricyclamol iodide... 

The solid-state photoreaction provided very high syn/anti stereoselectivity of 44b (syn/anti ratio 2.1 in solution and 60 in the solid-state, respectively). Furthermore, the solid-state photoreaction was found to give the syn-44b as a chiral compound in 81% ee however, the crystal system could not be determined. 

All-trans-perhydrotriphenylene (PHTP) (cf. insert in Figure 14) is the product of exhaustive hydrogenation of triphenylene. It belongs to one of ten stereoisomers of PHTP. The chiral compound of high rotational symmetry (D3 — C3 -h 3 C2) forms inclusion complexes. The stereoselective polymerization via 7-radiation of the prochiral diolelin 1,3-pentadiene within the chiral nano channels of (.R)-(-)-all-trans-PHTP led to an optically active 1,4-trans-isotactic polymer (Nattaand Farina, 1976) (cf. Figure 13). 

E. Productive and Destructive Stereoselective Reactions and the Preparation of Isomerically Pure Chiral Compounds... 

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