Selenium-based methodology

Numerous examples of an organometallic based methodology for the formation of selenophenes have been discussed. In these cases, a selenolate anion is formed in situ followed by cyclization. The application to selenophenes is due to the Brandsma group <83TL2203>. Indeed, when hydrocarbon (49) is first metallated and then treated with selenium, a mixture of (50) (46%) and (51) (42%) is formed after hydrolysis (Equation (11)). The base catalyzed isomerization of (50) to (51) is quantitative. 

Excellent and detailed treatments of the use of anomalous dispersion data in the deduction of phase information can be found elsewhere (Smith et al., 2001), and no attempt will be made to duplicate them here. The methodology and underlying principles are not unlike those for conventional isomorphous replacement based on heavy atom substitution. Here, however, the anomalous scatterers may be an integral part of the macromolecule sulfurs (or selenium atoms incorporated in place of sulfurs), the iron in heme groups, Ca++, Zn++, and so on. Anomalous scatterers can also be incorporated by diffusion into the crystals or by chemical means. With anomalous dispersion techniques, however, all data necessary for phase determination are collected from a single crystal (but at different wavelengths) hence non-isomorphism is less of a problem. 

The presence of asymmetric carbons in selenomethionine, other a-selenoamino acids, and related compounds produces different chiral enantiomers with different physiological activities. HPLC separation of enantiomers is possible with a range of chiral stationary phases, d- and 1-Selenomethionine enantiomers have been resolved with an a-cyclodextrin stationary phase and other species with a teicoplanin-based chiral phase. Hybrid chiral methodologies based on GC, HPLC, and capillary electrophoresis, coupled with ICP-MS are feasible. Enantiomers of d,l-selenocystine, d,l-selenomethio-nine, and d,l-selenoethionine were examined in a range of commercial dietary supplements using a chiral crown ether stationary phase and ICP-MS detection. Selenium-em-iched onion, garlic, and yeast were analyzed and some of the selenoamino acid enantiomers were identified. l-Fluoro-2, 4-dinitro-phenyl-5-l-alanine amide was used to derivatize enantiomers of selenoamides for enhanced resolution. 

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