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1
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0000851696
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Eds, B. M. Trost, I. Fleming, Pergamon Press, Oxford, and references therein
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C. H. Heathcock in Comprehensive Organic Synthesis (Eds.: B. M. Trost, I. Fleming), Pergamon Press, Oxford, 1991, vol. 2. pp. 133-180, and references therein.
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Comprehensive Organic Synthesis
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, pp. 133-180
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Heathcock, C.H.1
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3
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0343034826
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The boric acid mediated self-condensation of aldehydes requires fairly drastic conditions (refluxing xylenes). The reactions take up to 18 h to reach full conversion with heptanal: R. D. Offenhauer, S. F. Nelsen. J. Org. Chem. 1968, 33, 775-777.
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The boric acid mediated self-condensation of aldehydes requires fairly drastic conditions (refluxing xylenes). The reactions take up to 18 h to reach full conversion with heptanal: R. D. Offenhauer, S. F. Nelsen. J. Org. Chem. 1968, 33, 775-777.
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4
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34548335677
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These condensation reactions likely proceed according to Mannich- or Knoevenagel-type mechanisms. For examples of previous base- and acid-catalyzed Knoevenagel-Mannich-type reactions, see:a M. Shirai, Y. Yoshida, T. Furuya, S. Sadaike, JP2006045160, 2006;
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These condensation reactions likely proceed according to Mannich- or Knoevenagel-type mechanisms. For examples of previous base- and acid-catalyzed Knoevenagel-Mannich-type reactions, see:a) M. Shirai, Y. Yoshida, T. Furuya, S. Sadaike, JP2006045160, 2006;
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5
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34548357723
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R. M. Deshpande, M. M. Diwakar, R. V. Chaudhari, WO2005063668A1, 2005;
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b) R. M. Deshpande, M. M. Diwakar, R. V. Chaudhari, WO2005063668A1, 2005;
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6
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0942268593
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c) R. M. Deshpande, M. M. Diwakar, A. N. Mahajan, R. V. Chaudhari, J. Mol. Catal. A 2004, 211, 49-53;
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J. Mol. Catal. A
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Deshpande, R.M.1
Diwakar, M.M.2
Mahajan, A.N.3
Chaudhari, R.V.4
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7
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0032516288
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d) Y.-S. Hong, F. J. Chang, L. Lu, W.-C. Lin, Tetrahedron 1998, 54, 5233-5246:
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(1998)
Tetrahedron
, vol.54
, pp. 5233-5246
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Hong, Y.-S.1
Chang, F.J.2
Lu, L.3
Lin, W.-C.4
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8
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34548315016
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K. Matsuoka, JP04173757, 1992;
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e) K. Matsuoka, JP04173757, 1992;
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9
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34548309906
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Nagareda, K.: Yoshimura, N. JP 06263683, 1994. JP3324820, 2002;
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f) Nagareda, K.: Yoshimura, N. JP 06263683, 1994. JP3324820, 2002;
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10
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34548305684
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G. Duembgen, G. Fouquet, R. Krabetz, E. Lucas, F. Merger, F. Nees, EP0092097A1, 1983;
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g) G. Duembgen, G. Fouquet, R. Krabetz, E. Lucas, F. Merger, F. Nees, EP0092097A1, 1983;
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11
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34548322184
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G. Duembge, G. Fouquet, R. Krabetz, E. Lucas, F. Merger, F. Nees, DE3213681, 1983;
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h) G. Duembge, G. Fouquet, R. Krabetz, E. Lucas, F. Merger, F. Nees, DE3213681, 1983;
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13
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34548337736
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j) W. Bernhagen, H. Bach, E. Brundin, W. Gick, H. Springer, A. Hack, DE285504, 1980.
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(1980)
, vol.DE285504
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Bernhagen, W.1
Bach, H.2
Brundin, E.3
Gick, W.4
Springer, H.5
Hack, A.6
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14
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0001408311
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For examples of stoichiometric Mannich α-methylenations, see: k C. S. Marvel, R. L. Myers, J. H. Saunders, J. Am. Chem. Soc. 1948, 70, 1694-1699;
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For examples of stoichiometric Mannich α-methylenations, see: k) C. S. Marvel, R. L. Myers, J. H. Saunders, J. Am. Chem. Soc. 1948, 70, 1694-1699;
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15
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0042575666
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l) B. B. Snider, M. Lobera, T. P. Marien, J. Org. Chem. 2003, 68, 6451-6454;
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J. Org. Chem
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Snider, B.B.1
Lobera, M.2
Marien, T.P.3
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16
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10644249113
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this paper also includes an excellent introduction to the state-of-the-art methods for the synthesis of α-substituted acroleins
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m) K. Basu, J. Richards, L. A. Paquette, Synthesis 2004, 2841-2844, this paper also includes an excellent introduction to the state-of-the-art methods for the synthesis of α-substituted acroleins.
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(2004)
Synthesis
, pp. 2841-2844
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Basu, K.1
Richards, J.2
Paquette, L.A.3
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17
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0000388074
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For experimental examples with more complex aldehydes. see:a
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For experimental examples with more complex aldehydes. see:a) K. Yoshida, P. Grieco, J. Org. Chem. 1984, 49, 5257-5260;
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(1984)
J. Org. Chem
, vol.49
, pp. 5257-5260
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Yoshida, K.1
Grieco, P.2
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18
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0027142524
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b) R. Heckendorn, H. Allgeier, J. Baud, W. Gunzenhauser, C. Angst, J. Med. Chem. 1993, 36, 3721-3726.
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J. Med. Chem
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Heckendorn, R.1
Allgeier, H.2
Baud, J.3
Gunzenhauser, W.4
Angst, C.5
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19
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37049084069
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A particularly mild method based on dibromomethane has also been described: a Y.-S. Hon, F.-J. Chang, L. Lu, J. Chem. Soc., Chem. Commun. 1994, 2041-2042;
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A particularly mild method based on dibromomethane has also been described: a) Y.-S. Hon, F.-J. Chang, L. Lu, J. Chem. Soc., Chem. Commun. 1994, 2041-2042;
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20
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0032516288
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b) Y.-S. Hon, F.-J. Chang, L. Lu, W.-C. Lin, Tetrahedron 1998, 54, 5233-5246;
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(1998)
Tetrahedron
, vol.54
, pp. 5233-5246
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Hon, Y.-S.1
Chang, F.-J.2
Lu, L.3
Lin, W.-C.4
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22
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0034700029
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a) H. M. Boehm, S. Handa, G. Pattenden, L. Roberts, A. J. Blake, W.-S. Li. J. Chem. Soc. Perkin Trans. 1 2000, 3522-3538;
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J. Chem. Soc. Perkin Trans. 1
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Boehm, H.M.1
Handa, S.2
Pattenden, G.3
Roberts, L.4
Blake, A.J.5
Li, W.-S.6
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25
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0002863020
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b) S. Takano, K. Inomata, K. Samizu, S. Tomita, M. Yanase, M. Suzuki, Y. Iwabuchi, T. Sugihara, K. Ogasawara, Chem. Lett. 1989, 1283-1284.
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(1989)
Chem. Lett
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Takano, S.1
Inomata, K.2
Samizu, K.3
Tomita, S.4
Yanase, M.5
Suzuki, M.6
Iwabuchi, Y.7
Sugihara, T.8
Ogasawara, K.9
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26
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0028845540
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Total synthesis of brevetoxin B (second to last step): K. C. Nicolaou, F. P. J. T. Rutjes, E. A. Theodorakis, J. Tiebes, M. Sato, E. Untersteller, J. Am. Chem. Soc. 1995, 117, 1173-1174;
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a) Total synthesis of brevetoxin B (second to last step): K. C. Nicolaou, F. P. J. T. Rutjes, E. A. Theodorakis, J. Tiebes, M. Sato, E. Untersteller, J. Am. Chem. Soc. 1995, 117, 1173-1174;
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27
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0001065270
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see also
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see also: K. C. Nicolaou, K. R. Reddy, G. Skokotas, S. Fuminori, X.-Y. Xiao, J. Am. Chem. Soc. 1992, 114, 7935-7936.
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(1992)
J. Am. Chem. Soc
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, pp. 7935-7936
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Nicolaou, K.C.1
Reddy, K.R.2
Skokotas, G.3
Fuminori, S.4
Xiao, X.-Y.5
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28
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0037140769
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Total synthesis of laulimalide: M. T. Crimmins, M. G. Stanton, S. P. Allwein, J. Am. Chem. Soc. 2002, 124, 5958-5959;
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b) Total synthesis of laulimalide: M. T. Crimmins, M. G. Stanton, S. P. Allwein, J. Am. Chem. Soc. 2002, 124, 5958-5959;
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29
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0037453610
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c) A. Ahmed, E. K. Hoegenauer, V. S. Enev, M. Hanbauer, H. Kaehlig, E. Ohler, J. Mulzer, J. Org. Chem. 2003, 68, 3026-3042;
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J. Org. Chem
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Ahmed, A.1
Hoegenauer, E.K.2
Enev, V.S.3
Hanbauer, M.4
Kaehlig, H.5
Ohler, E.6
Mulzer, J.7
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30
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33645029445
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d) Pinnatoxin A: A. Ishiwata, S. Sakamoto, T. Noda, M. Hirama, Synlett 1999, 692-694.
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(1999)
Synlett
, pp. 692-694
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Pinnatoxin, A.1
Ishiwata, A.2
Sakamoto, S.3
Noda, T.4
Hirama, M.5
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32
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34548322183
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Further solvent screening with our first-generation catalyst system in the reaction between hydrocinnamaldehyde and formaldehyde had indicated that dichloromethane provides better reaction rates that our original solvent system
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Further solvent screening with our first-generation catalyst system in the reaction between hydrocinnamaldehyde and formaldehyde had indicated that dichloromethane provides better reaction rates that our original solvent system.
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33
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34548300478
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a becomes larger, the rate increases, presumably because the conjugate base of the benzoic acid is acting as a general base in the reaction. In the reaction mixture, the benzoic acids are expected to exist predominantly as their conjugate bases, and as such the use of the β term may be justified.
-
a becomes larger, the rate increases, presumably because the conjugate base of the benzoic acid is acting as a general base in the reaction. In the reaction mixture, the benzoic acids are expected to exist predominantly as their conjugate bases, and as such the use of the β term may be justified.
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34
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34548298385
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See the Supporting Information for full details of the reaction optimization
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See the Supporting Information for full details of the reaction optimization.
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36
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0032945520
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T. Ishikawa, E. Uedo, S. Okada, S. Saito, Synlett 1999, 450-452.
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(1999)
Synlett
, pp. 450-452
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Ishikawa, T.1
Uedo, E.2
Okada, S.3
Saito, S.4
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37
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34548325269
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No product was formed after 6 h with 10 mol-% of the catalyst with aldehyde 1g. However, the use of 20 mol-% of the catalyst promoted 86% conversion to 11g in the same time.
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No product was formed after 6 h with 10 mol-% of the catalyst with aldehyde 1g. However, the use of 20 mol-% of the catalyst promoted 86% conversion to 11g in the same time.
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38
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34548357722
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We used formaldehyde as 36.5 wt, solution in water. Under these conditions, the amount of formaldehyde was 16.5 μL. This would correlate to 10.5 μL of H2O under the reaction conditions
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2O under the reaction conditions.
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39
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34548318009
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[15]
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[15]
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40
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34548320110
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See p. 137 in ref.[1
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[1]
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42
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0037028550
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b) B. List, P. Polarjiev, W. T. Biller, H. J. Martin, J. Am. Chem. Soc. 2002, 124, 827-833;
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J. Am. Chem. Soc
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List, B.1
Polarjiev, P.2
Biller, W.T.3
Martin, H.J.4
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43
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0034654216
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for a discussion on the mechanistic explanation of the observed condensation side-product, see
-
c) for a discussion on the mechanistic explanation of the observed condensation side-product, see: B. List, R. A. Lerner, C. F. Barbas III, J. Am. Chem. Soc. 2000, 122, 2395-2396.
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J. Am. Chem. Soc
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List, B.1
Lerner, R.A.2
Barbas III, C.F.3
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44
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0034685977
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For the observation of a similar inverse relationship, see
-
For the observation of a similar inverse relationship, see: D. J. Parks, J. M. Blackwell, W. E. Piers, J. Org. Chem. 2000, 65, 3090-3098.
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J. Org. Chem
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Parks, D.J.1
Blackwell, J.M.2
Piers, W.E.3
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45
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0002502430
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The formation of an enamine species from the iminium cation is favored at least by a rate factor of 103 over the amine-catalyzed enolization reaction, see:a R. D. Roberts, H. E. Ferran Jr, M. J. Gula, T. A. Spencer, J. Am. Chem. Soc. 1980, 102, 7054-7058
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3 over the amine-catalyzed enolization reaction, see:a) R. D. Roberts, H. E. Ferran Jr, M. J. Gula, T. A. Spencer, J. Am. Chem. Soc. 1980, 102, 7054-7058:
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46
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2642643863
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b) D. J. Hupe, M. C. R. Kendall, T. A. Spencer, J. Am. Chem. Soc. 1972, 94, 1254-1263.
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Hupe, D.J.1
Kendall, M.C.R.2
Spencer, T.A.3
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47
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34548330424
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The previously determined β values for iminium → enamine conversions are in the ranae of 0.5-0.6. See ref.[22
-
[22]
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48
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34548337735
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In preliminary experiments, these catalyst systems are also active in the α-methylenation reactions with ketones. However, these products are much more sensitive to dimerization and oligomerization reactions than the corresponding aldehydes
-
In preliminary experiments, these catalyst systems are also active in the α-methylenation reactions with ketones. However, these products are much more sensitive to dimerization and oligomerization reactions than the corresponding aldehydes.
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49
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0026604467
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J. D. White, J. C. Amedio, S. Gut, S. Ohira, L. R. Jayasinghe, J. Org. Chem. 1992, 57, 2270-2284.
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H. Harada, T. Morie, Y. Hirokawa, S. Kato, Chem. Pharm. Bull. 1996, 44, 2205-2212.
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