Capture and release techniques

Product isolation and purification is often a difficult and time-consuming task. Capture and release techniques are useful to purify and isolate the products of complex multistep syntheses. The desired products are usually labeled with a tag that specifically binds to resins or a stationary phases applied in column chromatography. Binding can be covalent or by adsorption. By-products are easily removed by washing, followed by controlled release of the desired products. 

Scheme 20.24 Capture and release technique using resin-bound Fmoc-Cys-OH.

Procter and coworkers" have described a Sm(II)-mediated (106), asymmetric capture and release approach (Scheme 7.22) to y-butyrolactones (107) that involves intermolecular radical additions to a,[3-unsaturated esters (105) attached to resin through an ephedrine chiral linker (108). Resin capture-release is a hybrid technique that combines elements of traditional solid-phase synthesis and the use of supported reagents. Fukuzawa s Sm(II)-mediated, asymmetric method to y-butyrolactones was chosen to demonstrate the feasibility of such a process. y-Butyrolactones (107) were obtained by capture of a reactive intermediate from solution through an asymmetric transformation starting from a,p-unsaturated esters (105) immobilized on an ephedrine chiral resin. Lactone products were obtained in moderate yields with selectivities up to 96% ee. Nevertheless, the ephedrine resin can be efficiently reused for many cycles although in some cases lower yields were obtained on reuse of the chiral resin. 

The first report of resin capture in solution-phase chemical library synthesis involved the covalent capture of solution-phase Ugi reaction products onto a functionalized polystyrene resin.73 Excess reactants, reagents, and reagent byproducts were washed away from the resin-captured intermediates. Further manipulation and release afforded purified solution-phase products for screening. More recently the same group reported on resin capture as a technique for the preparation of tetrasubstituted olefin libraries.74 75 As illustrated in Scheme 5, m-vinyl di-boryl esters were reacted with aryl halides (R3ArX) in parallel Suzuki reactions, leading to solution-phase intermediates. Another Suzuki reaction, this time with the... 

Another example of the resin-capture-release technique which should see widespread applications in the future is the selenium-mediated functionalization of organic compounds. Polymer-supported selenium-derived reagents [34] are very versatile because a rich chemistry around the carbon-selenium bond has been established in solution and the difficulties arising from the odor and the toxicity of low-molecular weight selenium compounds can be avoided. Thus, reagent 26 (X = Cl) was first prepared by Michels, Kato and Heitz [35] and was employed in reactions with carbonyl compounds. This treatment yielded polymer-bound a-seleno intermediates, which were set free back into solution as enones from hydrogen peroxide induced elimination. Recently, new selenium-based functionalized polymers 26 (X = Br)-28 were developed, which have been utilized in syntheses according to Scheme 11 (refer also to Scheme 3) [36],... 

An extended application of the resin-capture-release technique is depicted in Scheme 13. With the help of reagent 31, a functionalized pyridine was captured as an acyl pyridinium cation 32 on a solid support which was followed by Grignard addition and hydrolysis under acidic conditions to afford polymer-supported N-acylated dehydropyridinones 33 [39]. Advantageously, any unreacted acylium complex collapses to the parent resin upon workup. These heterocycles, which ideally can serve as scaffolds, are then released under basic conditions. 

In many spills, cleaning stations are set up to rehabilitate birds. Although techniques have improved gready in the past few years, success rates are still poor as it is very stressful for a wild bird to be captured and handled. Less than half of the oiled birds that are cleaned and released actually survive. Only very sick birds can... 

Scheme 20.25 Cap and capture-release techniques applied to a trimannoside synthesis.

Wu J, Guo Z. Cap and capture-release techniques applied to solid-phase oligosaccharide synthesis. J Org Chem 2006 71 7067-7070. 

Possible solutions - Harvesting has much in common with brood-stock acquisition, in that it deals with concentrating and capturing sexually mature, i.e., marketable animals. In fact, the brood-stock is often sorted out from the harvested animals to start a new culture cycle. Attractive chemical cues, such as sex pheromones involved in chemical communication between adult crustaceans, might be integrated into the aforementioned harvesting techniques, to increase the efficiency and rapidity of animal capture and to reduce the stress and loss of animals associated with this action. For example, such chemical cues might be released from traps or the collection basin. 

In the case of gaseous contaminants, the tracer gas is selected to simu late as well as possible the properties (density, temperature) and momentum of the real contaminant. It is essential to ensure that the tracers arc nontoxic, chemically nonreactive, nonadsorptive on indoor surfaces, and inexpensive. The mixing of the tracer with the actual gaseous contaminant before its release or the release of the tracer with a density near that of the air will improve the validity of the simulation. With tracers, the most difficult task in practice is the relationship of the discharge between the tracer and the real contaminant. Case-by-case techniques to release the tracer are necessary in practice. With tracer gases, the procedure for capture efficiency is described in detail in the European Standard. - The tracer gas concentrations are measured in the exhaust duct for two release locations as illustrated in Fig. 10.108. 

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