Stereo-isomers

Recall from Section 7 13 that a stereospecific reaction is one in which each stereoiso mer of a particular starting material yields a different stereoisomeric form of the reaction product In the ex amples shown the product from Diels-Alder cycloaddi tion of 1 3 butadiene to as cinnamic acid is a stereo isomer of the product from trans cinnamic acid Each product although chiral is formed as a racemic mixture... 

Dehydrohalogenation of the diastereomenc forms of 1 chloro 1 2 diphenylpropane is stereo specific One diastereomer yields (E) 1 2 diphenylpropene and the other yields the Z isomer Which diastereomer yields which alkene" Why" ... 

It IS understood that a amino acids occur as their l stereo isomers unless otherwise indicated The d notation is explicitly shown when a D amino acid is present and a racemic amino acid is identified by the prefix dl... 

In this section we shall consider three types of isomerism which are encountered in polymers. These are positional isomerism, stereo isomerism, and geometrical isomerism. We shall focus attention on synthetic polymers and shall, for the most part, be concerned with these types of isomerism occurring singly, rather than in combination. The synthetic and analytical aspects of stereo isomerism will be considered in Chap. 7. Our present concern is merely to introduce the possibilities of these isomers and some of the vocabulary associated with them. 

Another anticonvulsant, formerly used as a hypnotic, is 5-ethyl-5-phenyIhydantoin [631 -07-2] (Nirvanol, Mephenytoin). Its S isomer is stereo-selectively eliminated in most subjects, a fact having clinical consequences with both desired and untoward effects (119). 

It would be pertinent to point out (25,27) that the trisubstituted isomer of the enamine of 2-aIkylcyclohexanone reacts in a quantitative manner with ethyl azodicarboxylate to give the addition product (35). This reaction in Conjunction with NMR spectroscopy can thus be employed for the determination of the amount of the trisubstituted isomer. According to the authors, hydrolysis of 35 furnishes the corresponding cw-2,6-disubstituted cyclohexanone (36) this seems unlikely since it would involve the stereo-electronically unfavored equatorial protonation of the enamine. 

In further modifications of these norprogestins, reaction of norethindrone with acetic anhydride in the presence of p-toluene-sulfonic acid, followed by hydrolysis of the first-formed enol acetate, affords norethindrone acetate (41). This in turn affords, on reaction with excess cyclopentanol in the presence of phosphorus pentoxide, the 3-cyclopentyl enol ether (42) the progestational component of Riglovic . Reduction of norethindrone affords the 3,17-diol. The 33-hydroxy compound is the desired product since reactions at 3 do not show nearly the stereoselectivity of those at 17 by virtue of the relative lack of stereo-directing proximate substituents, the formation of the desired isomer is engendered by use of a bulky reducing agent, lithium aluminum-tri-t-butoxide. Acetylation of the 33,173-diol iffords ethynodiol diacetate, one of the most potent oral proves tins (44). ... 

Sterblingswolle,/. dead wool, fallen wool. Stereochemie, /. stereochemistry, stereo-chemisch, a. stereochemical, -isomer, a. stereoisoincric. 

Representation of and the nomenclature for stereo-isomers are given in Appendix 1. 

Sulfinyldiene 40 reacts, regio- and stereo selectively, with methylacrylate in the presence of a catalyst, affording carbomethoxycyclohexene derivatives [45]. Among the catalysts examined, the best was lithium perchlorate used as a suspension in DCM it gave only endo isomers in 70% yield in a 96 4 d.e. ratio (Equation 3.11). 

It must be underlined that independently of the MS equipment characteristics, no information about stereo-chemistry can be obtained. In fact, cis and trans isomers of the corresponding carotenoid showed identical mass spectra, as did carotenoids with epoxide groups at 5,6 and 5,8 positions. In addition, special care should be taken in assigning carotenoid molecular masses to avoid confusion due to the various ions that may be formed depending on measurement conditions. 

Note that the 1,2-diequatorial substituted examples in Fig 7.10(c and d) are individual stereoisomers. The corresponding cis-species (Fig. 7.11b) is not another conformation, but another stereo isomer. The experimentally by calorimetry determined energy difference between the isomers is 6.5 kJ mol" . 

HES Hypereosinophilic syndrome HETE 5,8,9,11,12 and 15 Hydroxyeicosatetraenoic acid 5(S)HETE A stereo isomer of 5-HETE... 

Shannon 1983). and PCP-mimetic activity is exhibited stereo -specifically by the dextro isomer (Brady et al. 1982). 

Aliphatic acids such as butyric acid have been previously implicated as being allelopathic compounds (46, 47, 23). Chou and Patrick (23) isolated butyric acid from soil amended with rye and showed that it was phytotoxic. Hydroxy acids have also been shown to possess phytotoxic properties (48) but have not been implicated in any allelopathic associations. Since SHBA is a stereo isomer, and the enantiomer was not identified because of impurity, all bioassays were run using a racemic mixture. The D-(-) stereo isomer of SHBA has been isolated from both microorganisms and root nodules of legumes and is suspected to be a metabolic intermediate in these systems (49). It is likely that only one enantiomer was present in the extract therefore, the true phytotoxic potential of this compound awaits clarification of the phytotoxicity of the individual enantiomers. 

Stereo isomers have the same constitution, but a different spatial arrangement of their atoms they differ in their configuration. Two cases have to be distinguished geometric isomers (diastereomers) and enantiomers. 

Disilenes readily add halogens14,66 and active hydrogen compounds (HX), such as hydrogen halides,63,66 alcohols, and water,27 63 as well as hydride reagents, such as tin hydride and lithium aluminum hydride.66 These reactions are summarized in Scheme 9. The reaction of the stereo-isomeric disilene (E)-3 with hydrogen chloride and alcohols led to a mixture of E- and Z-isomers, but the reaction with chlorine gave only one of the two possible stereoisomers, thus indicating that the former two reactions proceed stepwise while the latter occurs without Si—Si rotation. 

Scheme 3 Asymmetric Heck coupling of 3,4-dihydrofuran and iodobenzene in the presence of Pd complexes 9-12 giving a mixture of regio and stereo isomers a) 2(R)-phenyl-2,3-dihydrofuran, b) 2(R)-phenyl-2,5-dihydrofuran c) 2(S)-phenyl-2,3-dihydrofuran d) 2(S)-phenyl-2,5-dihydrofuran.

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