Induced selectivity

In an intramolecular aldol condensation of a diketone many products are conceivable, since four different ends can be made. Five- and six-membered rings, however, wUl be formed preferentially. Kinetic or thermodynamic control or different acid-base catalysts may also induce selectivity. In the Lewis acid-catalyzed aldol condensation given below, the more substituted enol is formed preferentially (E.J. Corey, 1963 B, 1965B). 

The most valuable characteristic of the Patemo-Buchi reaction is the ability to set multiple stereocenters in one reaction and the development of diastereocontrolled reactions has been a major theme of research concerning this reaction. Stereocontrol can be envisioned to spring from either the carbonyl or the alkene and be controlled by either the substrate directly or by a chiral auxiliary. Little success has been achieved in substrate-induced selection by the carbonyl the most successful results were produced by... 

Unfortunately, in most of the previous examples, the extent of the asymmetry-induction was determined by chiroptical measurements (ORD, CD) that gave qualitative and not quantitative information. The NMR chiral shift efficiency of TRISPHAT 8 and other hexacoordinated phosphate anions was therefore considered as an excellent analytical tool to provide accurate measurement of the induced selectivity by NMR spectroscopy. 

Figure 7.43 General conceptual scheme to obtain a 2D correlation spectrum by inducing selective time-dependent spectral variations with an external perturbation (mechanical, electrical, chemical, magnetic, optical, thermal, etc.). After Noda [1006]. From I. Noda, Applied Spectroscopy, 44, 550-561 (1990). Reproduced by permission of the Society for Applied Spectroscopy...

The polymer can also be used to tailor the selectivity and sensitivity of the optical sensor due to enrichment of the analyte by the polymer material. Furthermore, the polymer may the permeable for gases but not by ions again inducing selectivity for certain analytes. Finally, the polymer can provide optical isolation against ambient light and thus prevent bleaching and light interference. 

Formation of /1-lactams by the reaction of an acid chloride, a SchifFbase and a tertiary amine (Eq. 62) appears to involve multiple pathways, some of which are very fast at higher temperatures. When conducted in open vessels in unmodified micro-wave ovens, high level irradiation leads to preferential formation of the trans -lactams (55%) whereas, at low power, the cis isomer was obtained as the only product (84%). The failure of the cis isomer to isomerize to the trans compounds is an example of induced selectivity. 

The answer is c. (Hardman, pp 996-997r 1145—1146. Ka tzung, p 8455 Metronidazole is often used to treat antibiotic-associated enterocolitis, especially when caused by C difficile. Vancomycin is no longer preferred because it induces selection of resistant staphylococci. Clindamycin is also associated with C difficile colitis, but in another way a higher percentage of patients taking this over other antibiotics develop antibiotic-associated enterocolitis. 

Spirocyclopropane isoxazolidines 75, obtained from alkylidenecyclopropane nitrones, underwent thermally induced selective rearrangement to pyrrolo[3,4-A]pyridinones 76 <00TA897>. The same adducts 75 in the presence of a protic acid afforded exclusively p-lactams 77 (57-60% yield) accompanied by ethylene extrusion <00JA8075>. 

COPISA [CO pressure induced selective adsorption] A process for separating carbon monoxide from the effluent gases from steel mills by a two-stage PSA unit. Developed jointly by Kawasaki Steel Corporation and Osaka Oxygen Industry. In the first stage, carbon dioxide is removed by activated carbon. In the second stage, carbon monoxide is removed by sodium mordenite. 

Kar S, Seto D, Dore D, Chabot J-G, Quirion R. 1997b. Systemic administration of kainic acid induces selective time-dependent decrease in [ Ijinsulin-like growth factor I, [ I] insulin-like growth factor II and [ I] insulin receptor binding sites in adult rat hippocampal formation. Neuroscience 80 1041-1055. 

In the first group definite states of the molecules to be analyzed are excited by the monochromatic and frequency-tunable laser light, thus inducing selective photochemical reactions. 

Mayani H., Dragowska W., Lansdorp P. (1993) Cytokines-induced selective expansion and maturation of erythroid versus myeloid pregenitors from purified cord blood precursor cells, BloodSUlZ), 3252-3258. 

Bugaut, A. Bathany, K. Scmitter, J.-M. Rayner, B. Target-induced selection of ligands from a dynamic combinatorial library of mono- and bi-conjugated oligonucleotides. Tetrahedron Lett. 2005, 46, 687-690. 

The notable mode of stereoselectivity of Cinchona alkaloids is presented by its psendoenantiomeric pairs which can be employed to generate either enantiomer of chiral prodnct. Key moieties that are central to Cinchona alkaloids are the quinuclidine nitrogen and the adjacent C(9)-OH (the N-C(8)-C(9)-OH moiety) (Fig. 2). In psendoentiomeric alkaloids in the natural open conformation, the torsion angle N-C(8)-C(9)-0 are opposite in sign Q and CD are (-), and thereby induce selectivity for one enantiomer, whereas QD and C are (-I-) and afford the other enantiomer [28, 29],... 

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