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16244385564
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note
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N2′-type, intramolecular nucleophilic attack on the proximal carbon of the allene moiety.
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43
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16244378824
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note
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We have already reported the formation of azetidines by NaH-mediated intramolecular animation of bromoallenes: see, ref. [2b].
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44
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0028150852
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To determine the intermediate of this tandem cyclization reaction, we investigated the stepwise reaction of the bromoallene 33. Treatment of the bromoallene 33 with NaH in DMF gave the pyrrolidine 37 in 86% yield. Reaction of 37 under the same reaction conditions as the one-pot reaction afforded the exo-cyclized product 34 (67%) and endo-cyclized product 35 (20%) in essentially the same product ratio. Related five-membered-ring formation by intramolecular amination of a carbon-carbon triple bond has been reported, see: a) Y. Tamaru, M. Kimura, S. Tanaka, S. Kure, Z. Yoshida, Bull. Chem. Soc. Jpn. 1994, 67, 2838-2849;
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