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for an extension of this methodology to the reaction with ketimines, see: c
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The vinylogous Mannich reaction with silyloxy furans developed by Akiyama et al. gave rise to the opposite absolute configuration in the Mannich products when 2-hydroxyaniline-based imines were employed (ref. [6]). The authors proposed a nine-membered chelate in the transition state of the reaction.
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The vinylogous Mannich reaction with silyloxy furans developed by Akiyama et al. gave rise to the opposite absolute configuration in the Mannich products when 2-hydroxyaniline-based imines were employed (ref. [6]). The authors proposed a nine-membered chelate in the transition state of the reaction.
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72
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A similar and significant effect of the influence of double-bond geometry of a silyl dienolate was observed by Kalesse et al. in B-(C6F 5)3-activated vinylogous aldol reactions to afford excellent diastereoselectivities with a 3Z-configured dienolate and only moderate diastereoselectivities with a 3E-configured dienolate. See: J. Hassfeld, M. Christmann, M. Kalesse, Org. Lett. 2001, 3, 3561
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3-activated vinylogous aldol reactions to afford excellent diastereoselectivities with a 3Z-configured dienolate and only moderate diastereoselectivities with a 3E-configured dienolate. See: J. Hassfeld, M. Christmann, M. Kalesse, Org. Lett. 2001, 3, 3561.
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73
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2O, and THF, the reaction proceeded to 40% conversion after 24 h at RT and to 56% conversion after 48 h at RT. ESIMS/MS samples were collected after 2, 24, and 48 h to identify complex m/z 1024. After 6 d, the reaction was complete.
-
2O, and THF, the reaction proceeded to 40% conversion after 24 h at RT and to 56% conversion after 48 h at RT. ESIMS/MS samples were collected after 2, 24, and 48 h to identify complex m/z 1024. After 6 d, the reaction was complete.
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74
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77
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84962407641
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A similar counterion pair to 10 containing the negatively charged chiral phosphate and positively charged silylated Mannich product was postulated and calculated in a Brønsted acid catalyzed Mannich reaction: M. Yamanaka, J. Itoh, K. Fuchibe, T. Akiyama, J. Am. Chem. Soc. 2007, 129, 6756.
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A similar counterion pair to 10 containing the negatively charged chiral phosphate and positively charged silylated Mannich product was postulated and calculated in a Brønsted acid catalyzed Mannich reaction: M. Yamanaka, J. Itoh, K. Fuchibe, T. Akiyama, J. Am. Chem. Soc. 2007, 129, 6756.
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M. C. Burla, R. Caliandro, M. Camalli, B. Carrozzini, G. L. Cascarano, L. De Caro, C. Giacovazzo, G. Polidori, R. Spagna, SIR2004, package for solving crystal structures by Direct and Patterson Methods, Istituto di Cristallografia, CNR and Dipartimento di Scienze della Terra, Università di Perugia (Italy); http://www.ic.cnr.it/sir2004.
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G. M. Sheldrick, SHELX-97, University of Göttingen, Göttingen (Germany), 1996;
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"A short history of SHELX": G. M. Sheldrick, Acta Crystallogr. 2008, A64, 112-122.
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