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note
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For a complete list of all urea and thiourea catalysts examined see the Supporting Information.
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40
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37049069958
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The role of the alcohol additive is presumably to generate HCN as the active nucleophile in the addition reaction, as is the case in thiourea-catalyzed Strecker reactions (ref 4). For other examples of the beneficial effect of alcohol additives on cyanosilylation of carbonyls see: (a) Hayashi, M.; Matsuda, N.; Oguni, N. J. Chem. Soc., Perkin Trans. 1 1992, 3135-3140.
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Reference 15d
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(c) Reference 15d.
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43
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note
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The corresponding N,N-di-n-butylamine- and N,N,-di-n-pentylamine- substituted catalysts afforded comparable conversion to 3d, but with slightly lower enantioselectivity (95%).
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44
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note
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For the preparation of 3d, see the Supporting Information.
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45
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21244506286
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note
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Dialkyl ketones are poor substrates in cyanosilylation reactions with 3d: 2-heptanone, 11% ee; cyclohexyl methyl ketone, <5% conversion.
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46
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0028802842
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Ketone enantioface selectivity dictated solely by electronic differentiation is well-precedented: (a) Corey, E. J.; Helal, C. J. Tetrahedron Lett. 1995, 36, 9153-9156.
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note
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The cyclohexylamine-derived analogue of 3d, which lacks the tertiary amine group, displayed no reactivity under the standard conditions.
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