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Isoquinuclidines have been obtained as products in Lewis acid catalyzed reactions and as a by-product in the Lewis base catalyzed Baylis-Hillman reaction of cyclohexenone with aldimines: a) G. Babu, P. T. Perumal, Tetrahedron 1998, 54, 1627;
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Recently, a direct aza-Diels-Alder reaction by covalent aminocatalysis was reported: H. Sunden, I. Ibrahem, L. Eriksson, A. Cordova, Angew. Chem. 2005, 117, 4955;
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49
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33845321350
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note
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A small shift of the keto-enol equilibrium is sufficient for a reaction, as the formed dienol will be extracted directly from the equilibrium. Other cyclic enones such as cyclopentenone showed no reactivity under these conditions.
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50
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33845284475
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note
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A large number of chiral Brønsted acids were tested. Table 1 shows only the general trend of reactivity.
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51
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33845340440
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note
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The use of other binol phosphates, other chlorinated and aromatic solvents, aliphatic aldimines, as well as the variation of catalyst loading and enone concentration resulted in inferior enantioselectivities.
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52
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33845319734
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note
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The X-ray crystal structure of the exo product is shown in the Supporting Information.
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53
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37049069423
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Examples of such a stepwise addition-cyclization mechanism have been reported earlier for the reaction of silylenol ethers with aldimines: a) T. N. Birkinshaw, A. B. Tabor, A. B. Holmes, P. R. Raithby, J. Chem. Soc. Chem. Commun. 1988, 1601;
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56
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note
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The rate-determining step of the reaction is presumably the dienol formation, as no considerable conversion was observed without the addition of Brønsted acid 2.
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