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For an overview regarding applications of Mannich reactions to the preparation of biologically active molecules and target-oriented synthesis, see:
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67849103721
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For disclosures regarding catalytic enantioselective VM reactions that include examples of alkyl-substituted aldimines, see: With i-Pr- and Cy-substituted aldimines
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For disclosures regarding catalytic enantioselective VM reactions that include examples of alkyl-substituted aldimines, see: With i-Pr- and Cy-substituted aldimines:
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20
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53549088683
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With two closely related n-alkyl-substituted aldimines
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(a) Akiyama, T.; Honma, Y.; Itoh, J.; Fuchibe, K. Adv. Synth Catal. 2008, 350, 399-402. With two closely related n-alkyl-substituted aldimines:
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Only aryl-substituted aldimines
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(b) Yamaguchi, A.; Matsunaga, S.; Shibasaki, M. Org. Lett. 2008, 10, 2319-2322. Only aryl-substituted aldimines:
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67849094230
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For reports on catalytic enantioselective aza-Diels-Alder reactions that include examples with alkyl-substituted aldimines, see: With only Cysubstituted aldimines
-
For reports on catalytic enantioselective aza-Diels-Alder reactions that include examples with alkyl-substituted aldimines, see: With only Cysubstituted aldimines:
-
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24
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0031980938
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With i-Pr- and Cysubstituted aldimines
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(a) Kobayashi, S.; Komiyama, S.; Ishitani, H. Angew. Chem., Int. Ed. 1998, 37, 979-981. With i-Pr- and Cysubstituted aldimines:
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With 2-propyl-substituted aldimine
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(b) Itoh, J.; Fuchibe, K.; Akiyama, T. Angew. Chem., Int. Ed. 2006, 45, 4796-4798. With 2-propyl-substituted aldimine:
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For a related catalytic enantioselective aza-Diels-Alder protocol, see: d
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For a related catalytic enantioselective aza-Diels-Alder protocol, see: (d) Sunden, H.; Ibrahem, I.; Eriksson, L.; Córdova, A. Angew. Chem., Int. Ed. 2005, 44, 4877-4880.
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For catalytic enantioselective Mannich-type reactions (not VM or aza-Diels-Alder) that include reactions of alkyl-substituted aldimines, see: (a) Ishitani, H.; Ueno, M.; Kobayashi, S. J. Am. Chem. Soc. 2000, 122, 8180-8186.
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37
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For use of a related N-arylimine in Zr-catalyzed Mannich reactions with silylketene acetals, see
-
For use of a related N-arylimine in Zr-catalyzed Mannich reactions with silylketene acetals, see: Ishitani, H.; Ueno, M.; Kobayashi, S. J. Am. Chem. Soc. 1997, 119, 7153-7154.
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39
-
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67849097315
-
-
To the best of our knowledge, there is only one reported example of a catalytic enantioselective Mannich reaction that involves a hetero-atom- containing imine benzyloxy acetaldehyde-derived imine, see ref 10b
-
To the best of our knowledge, there is only one reported example of a catalytic enantioselective Mannich reaction that involves a hetero-atom- containing imine (benzyloxy acetaldehyde-derived imine); see ref 10b.
-
-
-
-
40
-
-
67849090521
-
-
See the Supporting Information for details of ligand screening studies
-
See the Supporting Information for details of ligand screening studies.
-
-
-
-
41
-
-
0347129770
-
-
For a case involving an enantioselective conjugate addition of an enantiomerically enriched enone with a stereogenic center a to the reacting site, where use of an amino acid-based chiral phosphine catalyst results in enhancement of selectivity, see: (a) Cesati, R. R, de Armas, J, Hoveyda, A. H. J. Am.Chem. Soc. 2004, 126, 96-101. For an example where an enantioselective alkylation of an enantiomerically enriched allylic phosphate promoted by amino acid-based catalyst proceeds readily and selectively with only one of the substrate enantiomers, see
-
For a case involving an enantioselective conjugate addition of an enantiomerically enriched enone with a stereogenic center a to the reacting site, where use of an amino acid-based chiral phosphine catalyst results in enhancement of selectivity, see: (a) Cesati, R. R.; de Armas, J.; Hoveyda, A. H. J. Am.Chem. Soc. 2004, 126, 96-101. For an example where an enantioselective alkylation of an enantiomerically enriched allylic phosphate promoted by amino acid-based catalyst proceeds readily and selectively with only one of the substrate enantiomers, see:
-
-
-
-
43
-
-
67849128673
-
-
See the Supporting Information for details regarding the preparation and enantiomeric purity of chiral non-racemic aldehydes used in this study. The selectivity values shown in Table 4 are corrected
-
See the Supporting Information for details regarding the preparation and enantiomeric purity of chiral non-racemic aldehydes used in this study. The selectivity values shown in Table 4 are corrected.
-
-
-
-
45
-
-
67849104610
-
-
For accuracy in measuring small amounts of chiral ligand and Ag salt, transformations were performed in the presence of 5 mol % catalyst.
-
For accuracy in measuring small amounts of chiral ligand and Ag salt, transformations were performed in the presence of 5 mol % catalyst.
-
-
-
-
46
-
-
67849116858
-
-
Although the gram scale reaction shown in eq 1 was performed with 5 mol, catalyst, previous studies involving related Mannich-type processes indicate that lower catalyst loadings can be readily extended to larger scale transformations; for example, see ref 5
-
Although the gram scale reaction shown in eq 1 was performed with 5 mol % catalyst, previous studies involving related Mannich-type processes indicate that lower catalyst loadings can be readily extended to larger scale transformations; for example, see ref 5.
-
-
-
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47
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33846781519
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For a related oxidation process, see
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For a related oxidation process, see: Momiyama, N.; Yamamoto, Y.; Yamamoto, H. J. Am. Chem. Soc. 2007, 129, 1190-1195.
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84869573696
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As illustrated by the examples below, enantioselective VM reactions with aldimines derived from α,β-unsaturated aldehydes proceed to >98% conversion and in high diastereo- and enantioselectivity but in low yields. Control experiments point to product instability.
-
As illustrated by the examples below, enantioselective VM reactions with aldimines derived from α,β-unsaturated aldehydes proceed to >98% conversion and in high diastereo- and enantioselectivity but in low yields. Control experiments point to product instability.
-
-
-
-
49
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67849111523
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For other related examples of catalytic enantioselective additions promoted by this class of amino acid-based chiral ligands, see
-
For other related examples of catalytic enantioselective additions promoted by this class of amino acid-based chiral ligands, see:
-
-
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50
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0029764025
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