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As the enantiomeric ratios have not been calibrated, ratios higher than 200:1 are reported as >99.5:<0.5. The actual observed ratios were: for Table2, entry1 (with (S)- 3): 99.90:0.10, and for Table2, entry3 (with (R)- 3): 0.02:99.98. In addition, we have also prepared ent- 17 ((S)- 17), which gives 99.98:0.02 e.r. with (S)- 3). These are, to the best of our knowledge, the highest enantioselectivities reported for these conjugate addition processes. These results also indicate that catalyst 3 appears to be almost solely responsible for the sense of enantioinduction. Although 17 is chiral, the results indicate that achiral versions of 17 could also be conceived
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For kinetic evidence of the involvement of iminium intermediates in pyrrolidine-catalyzed aldehyde condensation reactions, see Ref.[9b]. For a full description of the solvents and alternative amine catalysts screened, see the Supporting Information. As the enantiomeric ratios have not been calibrated, ratios higher than 200:1 are reported as >99.5:<0.5. The actual observed ratios were: for Table2, entry1 (with (S)- 3): 99.90:0.10, and for Table2, entry3 (with (R)- 3): 0.02:99.98. In addition, we have also prepared ent- 17 ((S)- 17), which gives 99.98:0.02 e.r. with (S)- 3). These are, to the best of our knowledge, the highest enantioselectivities reported for these conjugate addition processes. These results also indicate that catalyst 3 appears to be almost solely responsible for the sense of enantioinduction. Although 17 is chiral, the results indicate that achiral versions of 17 could also be conceived.
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74
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79959512255
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Step1 (formation of 4) proceeds faster with unbranched aliphatic aldehydes than with branched aliphatic or aromatic aldehydes, thus precluding the addition of all three components at once
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Step1 (formation of 4) proceeds faster with unbranched aliphatic aldehydes than with branched aliphatic or aromatic aldehydes, thus precluding the addition of all three components at once.
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75
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38349178582
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For a review of iminium catalysis, including a discussion of the mechanism of iminium-catalyzed Knoevenagel condensations, see.
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For a review of iminium catalysis, including a discussion of the mechanism of iminium-catalyzed Knoevenagel condensations, see:, A. Erkkilä, I. Majander, P. M. Pihko, Chem. Rev. 2007, 107, 5416-5470.
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(2007)
Chem. Rev.
, vol.107
, pp. 5416-5470
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Erkkilä, A.1
Majander, I.2
Pihko, P.M.3
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76
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79959518612
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-1 have also been identified and they are presented in the Supporting Information. The reported binding energies were obtained from the gas-phase electronic energies
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-1 have also been identified and they are presented in the Supporting Information. The reported binding energies were obtained from the gas-phase electronic energies.
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77
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79959507609
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1HNMR analysis. A slight upfield shift for the vinylic protons of 4 g (Δδ=-0.017ppm for the α and -0.020ppm for the βproton) was observed in presence of 17 (see the Supporting Information). Further binding studies are in progress
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1HNMR analysis. A slight upfield shift for the vinylic protons of 4 g (Δδ=-0.017ppm for the α and -0.020ppm for the βproton) was observed in presence of 17 (see the Supporting Information). Further binding studies are in progress.
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