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| Although translation to solid-phase synthesis was gratifyingly straightforward for most of these reactions, interesting differences from the original solution-phase results were noted in certain cases. For example, application of the Pauson¨CKhand reaction (19, 33, 34) to solid support-bound enynes 3 showed a slight trend toward higher yields and diastereoselectivities for the cyclopentapyrrolidinone products 5 in most cases (Scheme 3). This trend was particularly evident in the case of the phenyl-substituted product 5b (74% vs. 64% yield, 70¡Ã30 vs. 50¡Ã50 DR). Recognizing that the choice of solvent is known to affect this reaction in solution (35), we hypothesized that the polystyrene matrix might provide a more hydrophobic reaction milieu than suggested by the CH3CN solvent used to induce the cycloaddition reaction. Consistent with this idea, when the corresponding solution-phase reaction was carried out in benzene or toluene, similarly improved diastereoselectivities were observed. The diastereoselectivity of the solid-phase reaction could also be further improved by changing the solvent to benzene or toluene. This finding highlights the influence of the solid support in ¡°solvent effects¡± on some reactions. |
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lgq101(½ð±Ò+20, ·ÒëEPI+1): лл 2011-06-24 17:29:51
Mally89(½ð±Ò+1): ¸ÐлӦÖú£¡~ 2011-06-24 21:36:20
lgq101(½ð±Ò+20, ·ÒëEPI+1): лл 2011-06-24 17:29:51
Mally89(½ð±Ò+1): ¸ÐлӦÖú£¡~ 2011-06-24 21:36:20
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