Scandium(III) catalysis of transimination reactions. Independent and constitutionally coupled reversible processes

Journal of the American Chemical Society

Volumn 127, Issue 15, 2005, Pages 5528-5539

  Giuseppone, Nicolas ^a   Schmitt, Jean Louis ^a   Schwartz, Evan ^a   Lehn, Jean Marie ^a  

^a UNIVERSITÉ LOUIS PASTEUR   (France)

Author keywords

[No Author keywords available]

Indexed keywords

AMINES; CATALYSIS; CATALYSTS; ORGANIC SOLVENTS;

CHEMICAL TRANSFORMATIONS; SCANDIUM(III) CATALYSIS; SINGLE AMINE; TRANSIMINATION REACTIONS;

SCANDIUM;

SCANDIUM;

ARTICLE; BINDING AFFINITY; CATALYSIS; CHEMICAL BOND; CHEMICAL REACTION; EQUILIBRIUM CONSTANT;

EID: 17644404350     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja042469q     Document Type: Article

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31. For zinc-catalyzed transimination in water, see: (a) Leach, B. E.; Leussing, D. L. J. Am. Chem. Soc. 1971, 93, 3377-3384. For acid-catalyzed transimination in water, see: (b) Polyakov, V. A.; Nelen, M. I.; Nazarpack-Kandlousy, N.; Ryabov, A. D.; Eliseev, A. V. J. Phys. Org. Chem. 1999, 12, 357-363. For amine exchange in Schiff-base complexes, see: (c) Lindoy, L. F. Q. Rev. 1971, 25, 379-391. (d) Olszewski, E. J.; Martin, D. F. J. Inorg. Nucl. Chem. 1965, 27, 345-351. (e) Verter, H. S.; Frost, A. E. J. Am. Chem. Soc. 1960, 82, 85-89. For amino exchange of hydrazones in metal complexes, see: (f) Dong, G.; Chun-ying, D.; Ke-liang, P.; Qingjin, M. J. Chem. Soc., Chem. Commun. 2002, 1096-1097.
32. For zinc-catalyzed transimination in water, see: (a) Leach, B. E.; Leussing, D. L. J. Am. Chem. Soc. 1971, 93, 3377-3384. For acid-catalyzed transimination in water, see: (b) Polyakov, V. A.; Nelen, M. I.; Nazarpack-Kandlousy, N.; Ryabov, A. D.; Eliseev, A. V. J. Phys. Org. Chem. 1999, 12, 357-363. For amine exchange in Schiff-base complexes, see: (c) Lindoy, L. F. Q. Rev. 1971, 25, 379-391. (d) Olszewski, E. J.; Martin, D. F. J. Inorg. Nucl. Chem. 1965, 27, 345-351. (e) Verter, H. S.; Frost, A. E. J. Am. Chem. Soc. 1960, 82, 85-89. For amino exchange of hydrazones in metal complexes, see: (f) Dong, G.; Chun-ying, D.; Ke-liang, P.; Qingjin, M. J. Chem. Soc., Chem. Commun. 2002, 1096-1097.
33. For zinc-catalyzed transimination in water, see: (a) Leach, B. E.; Leussing, D. L. J. Am. Chem. Soc. 1971, 93, 3377-3384. For acid-catalyzed transimination in water, see: (b) Polyakov, V. A.; Nelen, M. I.; Nazarpack-Kandlousy, N.; Ryabov, A. D.; Eliseev, A. V. J. Phys. Org. Chem. 1999, 12, 357-363. For amine exchange in Schiff-base complexes, see: (c) Lindoy, L. F. Q. Rev. 1971, 25, 379-391. (d) Olszewski, E. J.; Martin, D. F. J. Inorg. Nucl. Chem. 1965, 27, 345-351. (e) Verter, H. S.; Frost, A. E. J. Am. Chem. Soc. 1960, 82, 85-89. For amino exchange of hydrazones in metal complexes, see: (f) Dong, G.; Chun-ying, D.; Ke-liang, P.; Qingjin, M. J. Chem. Soc., Chem. Commun. 2002, 1096-1097.
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47. 3 times slower).
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50. 3, reactions intended to study the linear correlation between the initial rate and the catalyst concentration were performed in deuterated tetrachloroethane.
51. Experiments were set up for 10 different values of imine concentration from 0.05 equiv to 0.9 equiv (1.13, 4.52, 6.78, 9.04, 11.3, 13.6, 15.8, 18.1, and 20.3 mM) relative to the amine (22.6 mM; 4 mol % catalyst); and for eight different values of amine concentration from 0.1 equiv to 1.8 equiv (2.26, 4.52, 9.04, 18.4, 27.1, 36.2, and 40.7 mM) relative to the imine (22.6 mM; 4 mol % catalyst).
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53. A related behavior is found for carrier-mediated transport. See: Jacquez, J. A. Biochim. Biophys. Acta 1967, 79, 318-328. Also, in the transport of alkali ions by cryptates, the strongly bound potassium ions saturate the carrier and strongly decrease the transport rates, see: Kirch, M.; Lehn, J.-M. Angew. Chem. 1975, 87, 542-543; Angew. Chem., Int. Ed. Engl. 1975, 14, 555-556. Behr, J.-P.; Kirch, M.; Lehn, J.-M. J. Am. Chem. Soc. 1985, 107, 241-246.
54. A related behavior is found for carrier-mediated transport. See: Jacquez, J. A. Biochim. Biophys. Acta 1967, 79, 318-328. Also, in the transport of alkali ions by cryptates, the strongly bound potassium ions saturate the carrier and strongly decrease the transport rates, see: Kirch, M.; Lehn, J.-M. Angew. Chem. 1975, 87, 542-543; Angew. Chem., Int. Ed. Engl. 1975, 14, 555-556. Behr, J.-P.; Kirch, M.; Lehn, J.-M. J. Am. Chem. Soc. 1985, 107, 241-246.
55. A related behavior is found for carrier-mediated transport. See: Jacquez, J. A. Biochim. Biophys. Acta 1967, 79, 318-328. Also, in the transport of alkali ions by cryptates, the strongly bound potassium ions saturate the carrier and strongly decrease the transport rates, see: Kirch, M.; Lehn, J.-M. Angew. Chem. 1975, 87, 542-543; Angew. Chem., Int. Ed. Engl. 1975, 14, 555-556. Behr, J.-P.; Kirch, M.; Lehn, J.-M. J. Am. Chem. Soc. 1985, 107, 241-246.
56. A related behavior is found for carrier-mediated transport. See: Jacquez, J. A. Biochim. Biophys. Acta 1967, 79, 318-328. Also, in the transport of alkali ions by cryptates, the strongly bound potassium ions saturate the carrier and strongly decrease the transport rates, see: Kirch, M.; Lehn, J.-M. Angew. Chem. 1975, 87, 542-543; Angew. Chem., Int. Ed. Engl. 1975, 14, 555-556. Behr, J.-P.; Kirch, M.; Lehn, J.-M. J. Am. Chem. Soc. 1985, 107, 241-246.
57. The reaction described in Scheme 2 was performed at 25°C using deuterated cyclopentylamine and led to an identical initial rate as compared to the undeuterated amine.
58. Moreover, the reaction carried out under conditions that are typically used for constructing Hammett plots, that is, using the same constitutional mixture with a 4:1 ratio between 1 and each of the free amines, leads to a similar general behavior, with the product of the most strongly bound amine coming first, and the others following afterward.