Abstract
In 1986 Kagan, Agami et al.1 published a remarkable paper in the Journal of the American Chemical Society. The Freneh groups had studied asymmetric oxidation and aldol reactions* and they reported unique non-linear relationships between the enantiomerie excess (ee) of a chiral auxiliary and the ee of the product obtained in these reactions.1 In the titanium-mediated Sharpless epoxidation of geraniol (1) using diethyl tartrate (DET) as the ehiralligand (Seheme 2.1), the optieal purities of the epoxide (2) were signifieantly higher than the values calculated by assuming a linear relationship between tartrate and epoxide enantiomeric excesses (Figure 2.1, eurve b). In the asymmetric oxidation of methyl-p-tolyl sulfide (3) and in the proline-catalysed Robinson annulation of triketone (5) (Hajos-Parrish reaetion) (Seheme 2.1), negative deviations from linearity were observed (Figure 2.1, curve c).
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Bolm, C. (1996). Non-linear effects in enantioselective synthesis: asymmetric amplification. In: Stephenson, G.R. (eds) Advanced Asymmetric Synthesis. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-0797-9_2
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