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Chiral arsenic

Capillary Electrophoresis. Capillary electrophoresis (ce) or capillary 2one electrophoresis (c2e), a relatively recent addition to the arsenal of analytical techniques (20,21), has also been demonstrated as a powerful chiral separation method. Its high resolution capabiUty and lower sample loading relative to hplc makes it ideal for the separation of minute amounts of components in complex biological mixtures (22,23). [Pg.61]

In molecules in which the nitrogen atom is at a bridgehead, pyramidal inversion is of course prevented. Such molecules, if chiral, can be resolved even without the presence of the two structural features noted above. For example, optically active 12 (Trdger s base) has been prepared. Phosphorus inverts more slowly and arsenic still more slowly." Nonbridgehead phosphorus," arsenic, and antimony compounds have also been resolved... [Pg.130]

The most common structures of arsenic compounds are tetrahedral and pyramidal, which are similar when the sterically active lone pair is counted. Tetrahedral symmetry holds the potential for chirality and indeed many chiral organoarsenic compounds have been prepared. Arsenic may also use d orbitals for (d-d)n bonding and for hybridization with s2 and p3 orbitals, resulting in trigonal bipyramidal or octahedral structures. In the former the more electronegative substituents occupy the apical position. [Pg.239]

A wide range of bidentates containing one or more asymmetric phosphorus or arsenic donor atoms is now available due to the exploitation of a resolution technique involving the fractional crystallization of pairs of diastereomeric complexes formed by the chiral bidentates with pal-ladium(II) complexes containing optically active dimethyl(a-methylbenzyl)amine or dimethyl(l-ethyl-a-naphthyl)amine. Indeed, in recent work the two enantiomer pairs of l-(methylphenyl-arsino)-2-(methylphenylphosphino)benzene, (29a) and (29b), have been separated and isolated as optically pure air-stable crystalline solids with [a]o values of 79° (R, R ) and 15.5° (R, S ). 95... [Pg.199]

It is much more common for reactions to produce new chiral centers from achiral starting materials. Consequently, if we are to use the whole arsenal of synthetic methods available to us and at the same time produce single stereoisomers, then we must be able to control (or at least understand) the stereochemistry of reactions occurring at achiral centers. [Pg.144]

Pyrrolidinones with a chiral C-5 atom have been prepared in a very simple, one-pot synthesis, by treatment of TV-alkoxycarbamoyl y-amino a,/J-unsaturated carboxylates with Mg in methanol (equation 168)602. The products are formed in 87-95% yield, with high optical purity (96-99% ee). Since this y-lactam is very important, as an intermediate and target in the synthesis of natural products, this simple reaction is a very useful addition to the synthetic chemist s arsenal. Most other preparations of this target usually lead to racemic mixtures603-606. [Pg.753]

Optical activity was first observed with organic compounds having one or more chiral carbon atoms (or centres) (i.e. a carbon substituted with four different groups). In the structures (1) to (17) the chiral carbons are specified with an asterisk. Subsequently compounds having chiral centres at suitably substituted heteroatoms (e.g. silicon, germanium, nitrogen, phosphorus, arsenic, sulphur, etc.) were also synthesised. Molecular dissymmetry, and hence chirality, also... [Pg.5]

Considerable advances have been made in catalytic methodologies to perform asymmetric oxidations.1 3 Although no large-scale processes for commercial chiral pharmaceuticals currently use the technology, the methods are relatively new compared to catalytic asymmetric hydrogenation. The approach, however, is now in the synthetic arsenal, and it is surely just a matter of time before it comes to fruition as many drug candidates use asymmetric oxidations. An example of an up and coming asymmetric oxidation is the epoxidation method based on carbohydrate ketones (Chapter 10). [Pg.123]

Only one example of catalytic approach has been reported recently. The vast arsenal of chiral catalysts that is presently available, signals that future chapters dealing with this approach will be considerably well documented. [Pg.101]

New bases have also been proposed to extend the arsenal presented in Scheme 16. In particular, conformational constraints have been introduced on the amide. It was shown, for instance, that e.e. values up to 81% can be returned for the deprotonation of 4-f-butylcyclohexanone in a THF/HMPA mixture by a lithium amide derived from a tetrahydroquinoline bearing a heterocycle at C3102. Note that the same ketone can be converted in its (S)-enolate in 90% e.e. resorting to the bulky lithium A-trityl-A-(/ )-l-phenethylamide79. Interestingly, chiral lithium amides on polymeric solid support have also been successfully employed to deprotonate bridged cycloheptanones103. [Pg.541]

Ferrocene analogs that possess a heteroatom in place of one carbon atom have been known for some time. The most common of these heteroferrocenes are the azaferrocenes and the phosphaferrocenes, though complexes having snlfur, boron, arsenic, antimony, bismuth, and nickel atoms are known. Review articles that are either comprehensive (in the case of phosphaferrocenes), or cover aspects of this chemistry (in the case of azaferrocenes), are available space restrictions for this review do not permit complete coverage of these areas. Instead, recent developments in the area of planar chiral heteroferrocenes, especially as it relates to asymmetric catalyst design, will be the primary focus here. [Pg.2077]

Chiral phosphines are readily available from lithiated or palladated tertiary ferrocenylalkyl amines by reaction with chlorodiarylphosphine or chlorodialkyl-phosphine. As the chemistry of such phosphines is the topic of a separate chapter of this book (see Chapter 2), we will mention just a few aspects here. As with the phosphines, the corresponding derivatives of arsenic are obtained from chloro-diarylarsines [139],... [Pg.200]


See other pages where Chiral arsenic is mentioned: [Pg.116]    [Pg.114]    [Pg.116]    [Pg.114]    [Pg.53]    [Pg.201]    [Pg.209]    [Pg.213]    [Pg.954]    [Pg.763]    [Pg.516]    [Pg.219]    [Pg.249]    [Pg.249]    [Pg.64]    [Pg.912]    [Pg.915]    [Pg.13]    [Pg.24]    [Pg.762]    [Pg.1041]    [Pg.25]    [Pg.18]    [Pg.1544]    [Pg.355]    [Pg.245]    [Pg.53]    [Pg.44]    [Pg.98]    [Pg.92]    [Pg.337]    [Pg.100]    [Pg.39]    [Pg.245]    [Pg.27]    [Pg.215]   


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