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When N-chlorosuccinimide or N-fluorodi(benzenesulfonyl)- amine (0.5 equiv) was used as a source of electrophilic chloride or fluoride, 5 was obtained in a 1.3:1.0 or 1.2:1.0 syn/anti diastereoisomeric ratio, respectively, along with aldehyde 6 in nearly racemic form. These observations suggest that in the present system, C-C bond formation, rather than enamine formation, is both the rate- and enantiodetermining step. For a relevant discussion, see reference [13].
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3 substituent has a larger Charton value (n) than a tBu group (1.40 versus 1.24). For recent discussions on the use of Charton values in the context of asymmetric catalysis, see
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3 substituent has a larger Charton value (n) than a tBu group (1.40 versus 1.24). For recent discussions on the use of Charton values in the context of asymmetric catalysis, see: a) J. J. Miller, M. S. Sigman, Angew. Chem. 2008, 120, 783;
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Preliminary attempts to carry out the catalytic reactions in a tandem rather than sequential manner were successful with the achiral catalyst 1a but not with the chiral catalyst 1b. These studies are ongoing.
-
-
-
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