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1
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33747613399
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An example: formation of diastereomers using a covalent bond. In this case almost any available techniques can be used, such as fractional crystallization, distillation, sublimation or chromatography. See for instance:
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4
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0004219526
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Collins A.N., Sheldrake G.N., and Crosby J. (Eds), Wiley, New York
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In: Collins A.N., Sheldrake G.N., and Crosby J. (Eds). Chirality in Industry (1992), Wiley, New York
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(1992)
Chirality in Industry
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5
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0003807713
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Ahuja S. (Ed), American Chemical Society, Washington, DC
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In: Ahuja S. (Ed). Chiral Separations, Applications and Technology (1997), American Chemical Society, Washington, DC
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(1997)
Chiral Separations, Applications and Technology
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6
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0003846223
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Subramanian G. (Ed), Wiley-VCH, Weinheim
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In: Subramanian G. (Ed). Chiral Separation Techniques (2001), Wiley-VCH, Weinheim
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(2001)
Chiral Separation Techniques
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7
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0032544370
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Vries T., Wynberg H., van Echten E., Koek J., ten Hoeve W., Kellog R.M., Broxterman Q.B., Minnaard A., Kaptein B., van der Sluis S., Hulshof L., and Kooistra J. Angew. Chem., Int. Ed. Engl. 37 (1998) 2349-2354
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Vries, T.1
Wynberg, H.2
van Echten, E.3
Koek, J.4
ten Hoeve, W.5
Kellog, R.M.6
Broxterman, Q.B.7
Minnaard, A.8
Kaptein, B.9
van der Sluis, S.10
Hulshof, L.11
Kooistra, J.12
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8
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0004139082
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Krieger Publishing Co., Malabar, FL
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Jacques J., Collet A., and Wilen S.H. Enantiomers, Racemates and Resolutions (1994), Krieger Publishing Co., Malabar, FL
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(1994)
Enantiomers, Racemates and Resolutions
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Jacques, J.1
Collet, A.2
Wilen, S.H.3
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9
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85055171459
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An example: formation of diastereomers using strong electrostatic interactions as found in salts of chiral amines and acids. With some exceptions, the application of this approach is limited to fractional crystallization of diastereomeric salts. See for example:. Kozma D. (Ed), CRC Press, Boca Raton, FL
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An example: formation of diastereomers using strong electrostatic interactions as found in salts of chiral amines and acids. With some exceptions, the application of this approach is limited to fractional crystallization of diastereomeric salts. See for example:. In: Kozma D. (Ed). CRC Handbook of Optical Resolutions via Diastereomeric Salt Formation (2001), CRC Press, Boca Raton, FL
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(2001)
CRC Handbook of Optical Resolutions via Diastereomeric Salt Formation
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10
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33747591066
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note
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An example: formation of diastereomers using hydrogen bonding or weak/medium electrostatic interactions. Successful application of this approach for separation of enantiomers requires amplification (number of interactions) of these weak diastereomeric relationships, which can be achieved using HPLC of GC conditions. For references see: Ref. [1].
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11
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0037032309
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For new, fascinating crystallization techniques see:
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For new, fascinating crystallization techniques see:. Tamura R., Fujimoto D., Lepp Z., Misaki K., Miura H., Takahashi H., Ushio T., Nakai T., and Hirotsu K. J. Am. Chem. Soc. 124 (2002) 13139-13153
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Tamura, R.1
Fujimoto, D.2
Lepp, Z.3
Misaki, K.4
Miura, H.5
Takahashi, H.6
Ushio, T.7
Nakai, T.8
Hirotsu, K.9
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12
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33947298131
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Williams T., Pitcher R.G., Bommer P., Gutzwiller J., and Uskokovic M. J. Am. Chem. Soc. 91 (1969) 1871
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J. Am. Chem. Soc.
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Williams, T.1
Pitcher, R.G.2
Bommer, P.3
Gutzwiller, J.4
Uskokovic, M.5
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21
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33845374428
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Puchot C., Samuel O., Dunach E., Zhao S., Agami C., and Kagan H.B. J. Am. Chem. Soc. 108 (1986) 2353
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J. Am. Chem. Soc.
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Puchot, C.1
Samuel, O.2
Dunach, E.3
Zhao, S.4
Agami, C.5
Kagan, H.B.6
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22
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0000736403
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Kitamura M., Suga S., Niwa M., Noyori R., Zhai Z.-X., and Suga H. J. Phys. Chem. 98 (1994) 12776
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Kitamura, M.1
Suga, S.2
Niwa, M.3
Noyori, R.4
Zhai, Z.-X.5
Suga, H.6
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27
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33747602179
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note
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One of potential practical applications of this phenomenon might be the development of conceptually new and very economically efficient separation techniques.
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30
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0001045560
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Tsai T.-L., Herman K., Hug E., Rohde B., and Dreiding A.S. Helv. Chem. Acta 68 (1985) 2238
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Helv. Chem. Acta
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Tsai, T.-L.1
Herman, K.2
Hug, E.3
Rohde, B.4
Dreiding, A.S.5
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31
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0000650374
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Dobashi A., Motoyama Y., Kinoshita K., Hara S., and Fukasaku N. Anal. Chem. 59 (1987) 2209
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Anal. Chem.
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Dobashi, A.1
Motoyama, Y.2
Kinoshita, K.3
Hara, S.4
Fukasaku, N.5
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35
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0033807475
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Monde K., Harada N., Takasugi M., Kutschy P., Suchy M., and Dzurilla M. J. Nat. Prod. 63 (2000) 1312
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Monde, K.1
Harada, N.2
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Kutschy, P.4
Suchy, M.5
Dzurilla, M.6
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36
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0035356591
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Suchy M., Kutschy P., Monde K., Goto H., Harada N., Takasugi M., Dzurilla M., and Balentova E. J. Org. Chem. 66 (2001) 3940
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Suchy, M.1
Kutschy, P.2
Monde, K.3
Goto, H.4
Harada, N.5
Takasugi, M.6
Dzurilla, M.7
Balentova, E.8
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37
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0002636545
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Kosugi H., Abe M., Hatsuda R., Uda H., and Kato M. Chem. Commun. (1997) 1857
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(1997)
Chem. Commun.
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Kosugi, H.1
Abe, M.2
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Uda, H.4
Kato, M.5
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40
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85042258656
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Tanaka K., Osuga H., Suzuki H., Shogase Y., and Kitahara Y.J. Chem. Soc., Perkin Trans. 1 (1998) 935
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(1998)
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Tanaka, K.1
Osuga, H.2
Suzuki, H.3
Shogase, Y.4
Kitahara, Y.J.5
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41
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0033984729
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Ernholt B.V., Thomsen I.B., Lohse A., Plesner I.W., Jensen K.B., Hazell R.G., Liang X., Jacobsen A., and Bols M. Chem. Eur. J. 6 (2000) 278
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Chem. Eur. J.
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Ernholt, B.V.1
Thomsen, I.B.2
Lohse, A.3
Plesner, I.W.4
Jensen, K.B.5
Hazell, R.G.6
Liang, X.7
Jacobsen, A.8
Bols, M.9
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42
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33747603756
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For instance, in the most recent book (a) and review article (b) on non-conventional methods for resolution of enantiomers, this phenomenon not even mentioned:
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45
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33747586598
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note
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The following definitions are found in the literature: "self-amplification of optical activity", "enantiomer-differentiation", "autoseparation of enantiomers", "separation of excess enantiomer", "enantiomeric enrichment" and "optical purification".
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55
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33747607342
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note
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The initial observation of poor reproducibility in the ee's and therefore the phenomenon of self-disproportionation of enantiomers was noticed in 1995. when we discovered highly enantioselective DBU-catalyzed 1,3-PSR. However, at that time the problem was solved by using Schiff base 4 for direct determination of its enantiomeric purity.
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56
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33747599467
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note
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In three previous examples (see Ref. [19]) of self-disproportionation of enantiomers on achiral silica gel, the highest Δ% ee difference between the lowest and the highest % ee obtained, were: 83% (Ref. [19a]), 31% (Ref. [19b]), and 21% (Ref. [19c]).
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37049075389
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Soloshonok V.A., Kukhar V.P., Galushko S.V., Svistunova N.Y., Avilov D.V., Kuzmina N.A., Raevski N.I., Struchkov Y.T., Pisarevsky A.P., and Belokon Y.N. J. Chem. Soc., Perkin Trans. 1 (1993) 3143
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J. Chem. Soc., Perkin Trans.
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Soloshonok, V.A.1
Kukhar, V.P.2
Galushko, S.V.3
Svistunova, N.Y.4
Avilov, D.V.5
Kuzmina, N.A.6
Raevski, N.I.7
Struchkov, Y.T.8
Pisarevsky, A.P.9
Belokon, Y.N.10
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59
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8544244902
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Bravo P., Farina A., Kukhar V.P., Markovsky A.L., Meille S.V., Soloshonok V.A., Sorochinsky A.E., Viani F., Zanda M., and Zappala C. J. Org. Chem. 62 (1997) 3424
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J. Org. Chem.
, vol.62
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Bravo, P.1
Farina, A.2
Kukhar, V.P.3
Markovsky, A.L.4
Meille, S.V.5
Soloshonok, V.A.6
Sorochinsky, A.E.7
Viani, F.8
Zanda, M.9
Zappala, C.10
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60
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0000857641
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Soloshonok V.A., Kacharov A.D., Avilov D.V., Ishikawa K., Nagashima N., and Hayashi T. J. Org. Chem. 62 (1997) 3470-3479
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(1997)
J. Org. Chem.
, vol.62
, pp. 3470-3479
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Soloshonok, V.A.1
Kacharov, A.D.2
Avilov, D.V.3
Ishikawa, K.4
Nagashima, N.5
Hayashi, T.6
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61
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0030961675
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Soloshonok V.A., Avilov D.V., Kukhar' V.P., Meervelt L.V., and Mischenko N. Tetrahedron Lett. 38 (1997) 4671-4674
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Tetrahedron Lett.
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Soloshonok, V.A.1
Avilov, D.V.2
Kukhar', V.P.3
Meervelt, L.V.4
Mischenko, N.5
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62
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0030558966
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Taking into account a report by Katagiri et al. on strong enantiomer self-disproportionation of isopropyl 3,3,3-trifluoro-2-hydroxypropanoate during distillation, one may envision that amplification of this phenomenon by a trifluoromethyl group may be of much general nature and other achiral methods available for separation of organic compounds can be applied. In particular, our next goal will be studying the enantiomer self-disproportionation of various trifluoromethyl-containing compounds under sublimation conditions. For Katagiri's original publication, see:
-
Taking into account a report by Katagiri et al. on strong enantiomer self-disproportionation of isopropyl 3,3,3-trifluoro-2-hydroxypropanoate during distillation, one may envision that amplification of this phenomenon by a trifluoromethyl group may be of much general nature and other achiral methods available for separation of organic compounds can be applied. In particular, our next goal will be studying the enantiomer self-disproportionation of various trifluoromethyl-containing compounds under sublimation conditions. For Katagiri's original publication, see:. Katagiri T., Yoda C., Furuhashi K., Ueki K., Kubota T. Chem. Lett. 2 (1996) 115-116
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(1996)
Chem. Lett.
, vol.2
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Katagiri, T.1
Yoda, C.2
Furuhashi, K.3
Ueki, K.4
Kubota, T.5
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