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The selectivity factor, s, for kinetic resolution is defined as the ratio of the rate of reaction of the fast-reacting enantiomer of the racemic substrate, kfast, to the rate of reaction of the slow-reacting enantiomer, kslow, in the same transformation, i.e, s, kfast/kslow, The selectivity factor can be expressed in terms of enantiomeric excess (ee) of the remaining alcohol and the conversion (c) of the alcohol to the corresponding ketone, i.e, s, ln[(1- c)(1-ee)]/ln[(1- c)1 +ee, For s > 10, synthetically useful quantities of enantioenriched alcohol can be accessed. For example, an oxidative kinetic resolution with s, 10 at 62% conversion would afford recovery of alcohol of 90% ee. See also: Kagan, H. B, Fiaud, J. C. In Topics in Stereochemistry; Eliel, E. L, Ed, Wiley & Sons: New York, 1988; 18, pp 249-330
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slow). The selectivity factor can be expressed in terms of enantiomeric excess (ee) of the remaining alcohol and the conversion (c) of the alcohol to the corresponding ketone, i.e., s = ln[(1- c)(1-ee)]/ln[(1- c)(1 +ee)]. For s > 10, synthetically useful quantities of enantioenriched alcohol can be accessed. For example, an oxidative kinetic resolution with s = 10 at 62% conversion would afford recovery of alcohol of 90% ee. See also: Kagan, H. B., Fiaud, J. C. In Topics in Stereochemistry; Eliel, E. L., Ed.; Wiley & Sons: New York, 1988; Vol. 18, pp 249-330.
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See Supporting Information for details
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See Supporting Information for details.
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102
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0000323136
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(a) Wenkert, E.; Davis, L. L.; Mylari, B. L.; Solomon, M. F.; Da Silva, R. R.; Shulman, S.; Warnet, R. J.; Ceccherelli, D.; Curini, M.; Pellicciari, R. J. J. Org. Chem. 1982, 47, 3242.
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52049096917
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We have recently accomplished a formal synthesis of the naturally occurring enantiomer of amurensinine using a readily accessible diamine ligand that serves as a mimic for, -sparteine in the oxidative kinetic resolution. See: Ebner, D. C, Trend, R. M, Genet, C, McGrath, M. J, O'Brien, P, Stoltz, B. M Angew. Chem, Int. Ed. 2008, 47, 6367-6370
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We have recently accomplished a formal synthesis of the naturally occurring enantiomer of amurensinine using a readily accessible diamine ligand that serves as a mimic for (+)-sparteine in the oxidative kinetic resolution. See: Ebner, D. C.; Trend, R. M.; Genet, C.; McGrath, M. J.; O'Brien, P.; Stoltz, B. M Angew. Chem., Int. Ed. 2008, 47, 6367-6370.
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110
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0001412059
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A rationale for the observed selectivity follows from the calculated conformational equilibria of cis,cis-1,4-cyclooctadiene. See: Anet, F. A. L.; Yavari, I. J. Am. Chem. Soc. 1977, 99, 6986. Also see Supporting Information for a stereochemical model.
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A rationale for the observed selectivity follows from the calculated conformational equilibria of cis,cis-1,4-cyclooctadiene. See: Anet, F. A. L.; Yavari, I. J. Am. Chem. Soc. 1977, 99, 6986. Also see Supporting Information for a stereochemical model.
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111
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0346500606
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112
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53849116296
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The enantiomeric excess was determined after derivatization of lobeline by the method described in ref 21h. See Supporting Information for details
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The enantiomeric excess was determined after derivatization of lobeline by the method described in ref 21h. See Supporting Information for details.
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113
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53849089778
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Crooks and co-workers21h noted the rate of epimerization of diastereomerically pure cis-lobeline to 46:54 cis:trans-lobeline in various deuterated solvents by 1H NMR (CD3OD > CD3CN > CD3COCD3 > CDCl3, In our hands, the epimerization of diastereomerically pure cis-lobeline to 1:1 cis:trans-lobeline was much slower in C6D6 (5 days) as opposed to CDCl3 (2 days) and CD3OD 2 h
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3OD (2 h).
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