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Transition Metal-Mediated Cycloaddition and Cyclization Reactions. With the enyne and diyne substrates 3 and 4 in hand, we were poised to investigate the key transition metal-mediated solid-phase cycloaddition and cyclization reactions (Scheme 2). Although there are several examples of such reactions being carried out successfully on solid phase (20), many of these specific reactions had not been carried out on solid support previously, and none had been explored in the context of the TBDAS linker. However, we hoped that this linker would continue to mirror faithfully the previously established reactivity profile of the TBDPS protecting group used in the original solution-phase experiments.
Ring-closing metathesis (23) of enynes 3a,b,d proceeded uneventfully to vinylpyrrolines 8a,b,d. We had previously found in our solution-phase studies that, although these products were unreactive to most dienophiles, oxidation to the corresponding sulfonamides afforded more reactive dienes. Thus, these Diels¨C Alder reactions (24, 25) provided tricyclic benzodipyrrolidines 9a,b,d and isoindoline dicarboxylates 10a,b,d.

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lgq101(½ð±Ò+15, ·­ÒëEPI+1): ÔÙ´Îлл 2011-06-13 14:41:44
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