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Addition/cyclization of a bifunctional allylic reagent represents a strategic surrogate of the TMM cycloaddition reactions. For a recent example, see: Trost, B. M.; Bonk, P. J. J. Am. Chem. Soc. 1985, 107, 1778. van der Heide, T. A. J.; van der Bann, J. L.; de Kimpe, V.; Bickelhaupt, F.; Klumpp, G. W. Tetrahedron Lett. 1993, 34, 3309.
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note
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The reaction of 1 with N-acyl and N-tosyl imines gives γ-amino acid derivatives instead of [3 + 2] cycloadduct; to be published.
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39
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note
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In this respect, O-benzyloximes are superior to O-methoxime, because the former generally is obtained with higher anti selectivity (9:1) than the latter (7:3) by the reaction of an aldehyde and the corresponding alkoxyamine.
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40
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85085783372
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note
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13C labeled experiments, the methylene-labeled methylenecyclopropane i isomerized to the cyclopropane labeled ii prior to the cycloaddition, even when the reactive dimethyl fumarate was used as an acceptor. See also ref 10.
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41
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Huisgen, R. Angew. Chem., Int. Ed. Engl. 1963, 2, 633. See also: Trost, B. M.; Miller, M. L. J. Am. Chem. Soc. 1988, 110, 3687.
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Huisgen, R. Angew. Chem., Int. Ed. Engl. 1963, 2, 633. See also: Trost, B. M.; Miller, M. L. J. Am. Chem. Soc. 1988, 110, 3687.
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See for a single electron-transfer pathway of the TMM cycloaddition: Yamago, S.; Ejiri, S.; Nakamura, M.; Nakamura, E. J. Am. Chem. Soc. 1993, 115, 5344.
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syn larger than 2.6 and suggested the importance of the magnitude of the difference. See: Trost, B. M.; Miller, M. L. J. Am. Chem. Soc. 1988, 110, 3687. Whatever the threshold may be, the 67-fold rate difference in the present cycloaddition is a clear indication of the concertedness of the cycloaddition.
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The stereo specificity of the C=N cannot be certified in the presence example. Though the stereospecificity of cycloaddition has been considered to be a reliable criterion for the concertedness of the cycloaddition, recent studies by Zewail on the retro-Diels-Alder reaction revealed that the time scale of this conventional criteria is too slow to certify the concertedness: Horn, B. A.; Herek, J. L.; Zewail, A. H. J. Am. Chem. Soc. 1996, 118, 8755.
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