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Analogous experiments corresponding to entries 2, 3, and 5 (substrates 7a, 7b, and 7d, respectively) in Table 1 employing Cu(OTf)2/(S,S)-2,2′-isopropylidene-bis(4-phenyl-2-oxazoline) as the chiral Lewis acid were also conducted. Although a similar trend of increasing enantioselectivity with increasing size of the fluxional group was observed, the enantioselectivities were significantly lower in each case. The following enantioselectivities and endo:exo ratios were obtained with this ligand: (1) for substrate 7a, 28% ee, 88:12 endo:exo; (2) for substrate 7b, 38% ee, 91:09 endo:exo; and (3) for substrate 7d, 46% ee, 86:14 endo:exo. The sense of absolute stereochemistry of the cycloadducts was identical to that obtained with ligands 9-13
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Analogous experiments corresponding to entries 2, 3, and 5 (substrates 7a, 7b, and 7d, respectively) in Table 1 employing Cu(OTf)2/(S,S)-2,2′-isopropylidene-bis(4-phenyl-2-oxazoline) as the chiral Lewis acid were also conducted. Although a similar trend of increasing enantioselectivity with increasing size of the fluxional group was observed, the enantioselectivities were significantly lower in each case. The following enantioselectivities and endo:exo ratios were obtained with this ligand: (1) for substrate 7a, 28% ee, 88:12 endo:exo; (2) for substrate 7b, 38% ee, 91:09 endo:exo; and (3) for substrate 7d, 46% ee, 86:14 endo:exo. The sense of absolute stereochemistry of the cycloadducts was identical to that obtained with ligands 9-13.
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Experimental details, analysis, and spectra for nOe experiments are provided in the Supporting Information
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Experimental details, analysis, and spectra for nOe experiments are provided in the Supporting Information.
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2, bisoxazoline 10. and pyrazolidinone substrate 7d showed no line broadening with lower temperature (from room temperature to -35 °C), suggesting nitrogen inversion is sufficiently rapid that it is not observed on the NMR time scale.
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2, bisoxazoline 10. and pyrazolidinone substrate 7d showed no line broadening with lower temperature (from room temperature to -35 °C), suggesting nitrogen inversion is sufficiently rapid that it is not observed on the NMR time scale.
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