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The fact that the aldehydic products 5 resist further aldol reaction under proline catalysis provides another example of chemoselectivity. This crucial observation set the stage for a two-step de novo synthesis of carbohydrates
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The fact that the aldehydic products 5 resist further aldol reaction under proline catalysis provides another example of chemoselectivity. This crucial observation set the stage for a two-step de novo synthesis of carbohydrates: A. B. Northrup, D. W. C. Mac Millan, Science 2004, 305, 1752-1755.
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For a recent example of chemoselective cross-aldol reaction controlled by electronic factors using a primary amine as organocatalyst, see: M. Markert, U. Scheffletr, R. Mahrwald, J. Am. Chem. Soc. 2009, 131, 16642-16643.
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In water/octanol (1:1) systems n-butanal partitions into the aqueous phase approximately 1000 times more favorably than n-decanal (logD 0.88 vs 4.008), see
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In water/octanol (1:1) systems n-butanal partitions into the aqueous phase approximately 1000 times more favorably than n-decanal (log D 0.88 vs 4.008), see: R. Benigni, L. Conti, R. Crebelli, A. Rodomonte, M. R. Vari, Environ. Mol. Mutagen. 2005, 46, 268-280.
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For the first report on the conjugated addition of aldehydes to nitroalkenes catalyzed by O-protected prolinol B, see.
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For the first report on the conjugated addition of aldehydes to nitroalkenes catalyzed by O-protected prolinol B, see.
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For the first use of catalyst B.
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Y. Hayashi, H. Gotoh, T. Hayashi, M. Shoji, Angew. Chem. Int. Ed. 2005, 44, 4212-4215. For the first use of catalyst B.
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33751571805
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The conjugate additions catalyzed by B in the presence of water generally take place in the concentrated substrate phase, see, The 'perfectly suited' role of catalyst B in selectively promoting the conjugate addition synergistically combines with the inertness toward the homo-aldol reaction of aldehydes. This behavior may explain the absence of byproducts such as 12 that would consume the more hydrophobic aldehydic component 6.
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The conjugate additions catalyzed by B in the presence of water generally take place in the concentrated substrate phase, see: A. Carlone, M. Marigo, C. North, A. Landa, K. A. Jørgensen, Chem. Commun. 2006, 4928-4930. The 'perfectly suited' role of catalyst B in selectively promoting the conjugate addition synergistically combines with the inertness toward the homo-aldol reaction of aldehydes. This behavior may explain the absence of byproducts such as 12 that would consume the more hydrophobic aldehydic component 6.
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Decreasing the pH of the buffer from 8.0 to 7.0 resulted in greater selectivity for the desired "cross" cascade product over the undesired "homo" products, but other side reactions, such as aldol-type reactions of the aldehydes and the conjugate addition of nitromethane to the nitroalkene intermediate, increased. As the buffer pH dropped below 7.0, the rate, selectivity, and yield of the reaction decreased along with pH. Below a pH of approximately 6.5 (near the isoelectric point of proline), the first step of the reaction was strongly inhibited.
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Decreasing the p H of the buffer from 8.0 to 7.0 resulted in greater selectivity for the desired "cross" cascade product over the undesired "homo" products, but other side reactions, such as aldol-type reactions of the aldehydes and the conjugate addition of nitromethane to the nitroalkene intermediate, increased. As the buffer p H dropped below 7.0, the rate, selectivity, and yield of the reaction decreased along with p H. Below a p H of approximately 6.5 (near the isoelectric point of proline), the first step of the reaction was strongly inhibited.
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