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34
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0037894207
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-
note
-
In toluene the absence of an amine produced a dramatic drop in stereoselectivity (54% de for 4a, Table 1, entry 15). The de also decreased when DABCO was used in a catalytic amount (86% for 4a, Table 1, entry 13).
-
-
-
-
35
-
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0038231747
-
-
note
-
Faster reactions were also observed when DABCO was used instead of TEA, DIPEA, or TMP.
-
-
-
-
36
-
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0037556306
-
-
note
-
The crystal structures of 4j and 4n will be published in a full paper.
-
-
-
-
37
-
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0024430786
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-
The asymmetric addition of chiral alcohols to ketenes ("Merck reaction"), a conceptually related reaction, shows a very similar dependence on the polarity of the solvent and the structure of the catalyst (the amine base). See, for example: a) R. D. Larsen, E. G. Corley, P. Davis, P. J. Reider, E. J. J. Grabowski, J. Am. Chem. Soc. 1989, 111, 7650-7651;
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see also: b) B. L. Hodous, J. C. Ruble, G. C. Fu, J. Am. Chem. Soc. 1999, 121, 2637-2638;
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Calmes, M.1
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41
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0034820602
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The tight zwitterionic termolecular (alcohol/ketene/amine) intermediate that was recently proposed to explain the high stereocontrol of the Merck reaction might also be a useful model for a mechanistic interpretation of the reaction presented herein. The latter reaction is probably more complex both from a mechanistic and a stereochemical point of view because of the presence of a double stereoinduction effect: e) C. E. Cannizzaro, T. Strassner, K. N. Houk, J. Am. Chem. Soc. 2001, 123, 2668-2669.
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Cannizzaro, C.E.1
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