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33646787682
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For reviews on carbohydrate chiral auxiliary, see:
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17
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33646756061
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For reviews on carbohydrate chiral ligand, see:
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31
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33646771217
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note
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1H NMR, which can rule out the possibility of epimerization after the nucleophilic substitution reaction.
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-
-
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38
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33646757099
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When we prepared diacetone-d-glucose bound α-halo esters from racemic α-halo carboxylic acid derivatives, we obtained 5 and 6 with 69:31 dr and 73:27 dr, respectively. Formation of anything other than a 1:1 mixture of diastereomers can be explained by dynamic resolution of α-halo acids in the ester bond formation with chiral auxiliary. Alternatively, the in situ preparation of a ketene from α-halo acid halides and its treatment with a chiral auxiliary can afford diastereomerically enriched α-halo esters. For examples, see:
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41
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1042275590
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The 55:45 diastereomeric mixture of 6 is prepared by column chromatography with fractional collection
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Cardillo G., Fabbroni S., Gentilucci L., Perciaccante R., and Tolomelli A. Tetrahedron: Asymmetry 15 (2004) 593 The 55:45 diastereomeric mixture of 6 is prepared by column chromatography with fractional collection
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42
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33646789012
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-
note
-
When nucleophiles such as tritylthiol, sodium malonate, sodium 3,5-dimethoxyphenoxides, and potassium 6-flavonoxide were used for the reaction with 1 or 2, the corresponding substitution products were obtained in 76-94% yields with diastereomeric ratios from 69:31 to 54:46.
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44
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