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For the deprotection of allylic amines through isomerization reactions with Grubbs' catalysts, see:
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Snapper and co-workers described one example of the preparation of a tosyl enamide by means of his RCM-isomerization protocol (see ref 11a).
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33645546175
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note
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See Supporting Information for experimental details.
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43
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33645535704
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note
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The different behavior of toluene as solvent had already been observed by Fürstner in some RCM processes. He hypothesized that competing interactions between the mesityl group and aromatic solvents might reduce the stabilizing effect of the intramolecular π-π stacking with the benzylidene substituent; as a result, the catalyst would have more conformational freedom and therefore could display a different reactivity. See ref 6.
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44
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33645545193
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note
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Double bond isomerization prior to the RCM has been observed in several reports. See ref 10.
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-
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45
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33645542772
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note
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The preparation of nonfluorinated analogues to 6 has been described through a tandem isomerization-RCM of enynes, the inverse process of that described here. See ref 10d.
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46
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19544380068
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The synthesis of nonfluorinated cyclic enamides via copper-catalyzed intramolecular vinylation of amides was described very recently. However, this method does not afford rings with more than seven members, and it is greatly affected by the basicity of the substituent on the nitrogen atom. Our method thus circumvents the problems of this approach. See: Hu. T.; Li, C. Org. Lett. 2005, 7, 2035-2038.
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Ru-hydride species are known to catalyze olefin isomerization: (a) Wakamatsu, H.; Nishida, M.; Adachi, N.; Mori, M. J. Org. Chem 2000, 65, 3966-3970 and references therein.
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50
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33645553250
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note
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A theoretical study of the mechanism of these reactions is currently underway in our laboratory and will be published in due course.
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51
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33645553538
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note
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2-allyl grouping to undergo isomerization processes: (Diagram presented)
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52
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33645555012
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note
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In this case, δ-lactam 14 would arise from the result of a double isomerization in the nonfluorinated precursor 22. In contrast, no six-membered lactam was detected in the case of fluorinated derivatives, which indicates that the double bond isomerization catalyzed by ruthenium catalyst 2 does not take place on the difluoroolefinic chain.
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15044355873
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4 must be used as additive in this case because of the presence of a free amine group], pyrrol 41 was the only product isolated, arising from the aromatization of the isomerized product in the workup procedure. The same results were obtained when we started from the 2,5-dihydropyrrol 42 previously synthesized by RCM in a two-step sequence as described by Yang et al. See: Yang, Q.; Xiao, W.-J.; Yu, Z. Org. Lett. 2005, 7, 871 -874. It is assumed that the basicity of the nitrogen atom plays an important role in the nature of the final product. The presence of an electron-withdrawing group in the nitrogen atom prevents the dehydrogenation step towards the corresponding pyrrole.
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33645550302
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note
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11b only 30% of the isomerization product 6a was observed even after continuous heating of the reaction flask for 1 week.
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Fustero, S.; Navarro, A.; Pina, B.; García Soler, J.; Bartolomé, A.; Asensio, A.; Simón, A.; Bravo, P.; Fronza, G.; Volonterio, A.; Zanda, M. Org. Lett. 2001, 3, 2621-2624.
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33645547337
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note
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Similar results were also obtained in a two-step sequence in which the initially formed, nonisomerired metathesis product was treated with catalyst 2 in refluxing toluene: (Diagram presented)
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