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Ti(IV) is known to promote imine formation. (a) Weingarten, H.; Chupp, J. P.; White, W. A. J. Org. Chem. 1967, 32, 3246-3249. (b) Desai, M. C.; Thadeio, P. F. Tetrahedron Lett. 1989, 30, 5223-5226. In a blank experiment we proved that an aqueous acidic solution of Ti(IV) is much more efficient than an aqueous acidic solution of Ti(III) in promoting imine formation.
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14844345084
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note
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+) or as a N-Ti(IV)-complexed imine.
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24
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14844347970
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This sensitivity to steric hindrance is in line with a crowded transition state due to Ti(IV) complexation rather than imine protonation
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14844366360
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Additional N-alkylation was not observed with the other more volatile and/or less reactive alkyl iodides. In fact, by extracting the reaction mixture with EtOAc prior to neutralization of the aqueous acidic solution, the C-alkylated products were isolated in their protonated form. Further concentration of the organic extracts, at a reduced pressure, allowed elimination of the excess RI, thus hampering the additional N-alkylation, which may occur during further basic workup.
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