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N-Methoxyamides and N-phthalimidoamides are also known to generate stable acyl-nitrenium intermediates. (a) Falvey, D. E.; Kung, A. C. J. Org. Chem. 2005, 70, 3127-3132.
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It is known that terminal triple bonds react with PIFA to render α-hydroxyketones. Therefore, in our case, that position must be blocked for a successful transformation. Tamura, Y.; Yakura, T.; Haruta, J.-I.; Kita, Y. Tetrahedron Lett. 1985, 26, 3837-3840.
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3Al and the corresponding amine.
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3Al and the corresponding amine.
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37
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0142166022
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For the preparation of carboxylic acid 3b, see: Arcadi, A.; Cacchi, S.; Delmastro, M.; Marinella, F. Synlett 1991, 409-411.
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(b) For the preparation of carboxylic acid 3b, see: Arcadi, A.; Cacchi, S.; Delmastro, M.; Marinella, F. Synlett 1991, 409-411.
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38
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26844576835
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For a recent review on amide bond formation, see
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33846989166
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The preparation and cyclization of amide 4a to afford pyrrolidinone 5a has already been performed see ref 1, It is included here for comparative purposes
-
The preparation and cyclization of amide 4a to afford pyrrolidinone 5a has already been performed (see ref 1). It is included here for comparative purposes.
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40
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0346970844
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2OH, was crucial for the success of the reaction. For a revision about the chemical properties and synthetic uses of trifluoroethanol and other related solvents, see: Bégué, J.-P.; Bonnet-Delpon, D.; Crousse, B. Synlett 2004, 18-29.
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2OH, was crucial for the success of the reaction. For a revision about the chemical properties and synthetic uses of trifluoroethanol and other related solvents, see: Bégué, J.-P.; Bonnet-Delpon, D.; Crousse, B. Synlett 2004, 18-29.
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41
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0028050128
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It is noteworthy that the present access to 5-aroylpyrrolidines of type 5 offers many advantages over other alternatives described in the literature that involve multistep syntheses (chlorination plus Friedel-Craft acylation) starting from pyroglutamic acid or related derivatives, a process that lacks of regioselectivity when substituted arenes are employed. Rigo, B.; El Ghammarti, S.; Gautret, P.; Couturier, D. Synth. Commun. 1994, 24, 2597-2607.
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(a) It is noteworthy that the present access to 5-aroylpyrrolidines of type 5 offers many advantages over other alternatives described in the literature that involve multistep syntheses (chlorination plus Friedel-Craft acylation) starting from pyroglutamic acid or related derivatives, a process that lacks of regioselectivity when substituted arenes are employed. Rigo, B.; El Ghammarti, S.; Gautret, P.; Couturier, D. Synth. Commun. 1994, 24, 2597-2607.
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It was additionally verified that the formation of a related pyrrolidine derivative by application of the cyclization conditions to N-methyl-4-pentenamide was not possible. Instead, a 5-hydroxymethyl-4,5- dihydrofuranone was the only identified product. Examples of this type of transformation can be found in: Takahata, H, Suzuki, T, Maruyama, M, Moriyama, K, Mozumi, M, Takamatsu, T, Yamazaki, T. Tetrahedron 1988, 44, 4777-4786
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(b) It was additionally verified that the formation of a related pyrrolidine derivative by application of the cyclization conditions to N-methyl-4-pentenamide was not possible. Instead, a 5-hydroxymethyl-4,5- dihydrofuranone was the only identified product. Examples of this type of transformation can be found in: Takahata, H.; Suzuki, T.; Maruyama, M.; Moriyama, K.; Mozumi, M.; Takamatsu, T.; Yamazaki, T. Tetrahedron 1988, 44, 4777-4786.
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N-Alkylnitrenium ions would not be stable enough to exist.
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N-Alkylnitrenium ions would not be stable enough to exist.
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44
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