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Ring-opening reactions of oxa- and aza-bicyclic compounds proceed by a distinctively different mechanism that is initiated by a carbometalation of the strained double bond followed by either β-alkoxide or β-amide elimination, respectively. For leading references see: a) M. Lautens, K. Fagnou, S. Hiebert, Acc. Chem. Res. 2003, 36, 48-58;
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Partial epimerization of the stereocenter a to the carbonyl group was observed at higher temperature (130°C) and prolonged reaction, times (> 24 h) or when stronger bases (NaOrBu) were used
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Partial epimerization of the stereocenter a to the carbonyl group was observed at higher temperature (130°C) and prolonged reaction, times (> 24 h) or when stronger bases (NaOrBu) were used.
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47
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77953666162
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int, = 0.078), R(all) = 0.0806, wR(gt) = 0.1411. CCDC 770255 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/datajequest/cif
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48
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See the Supporting Information for determination of the absolute configuration
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See the Supporting Information for determination of the absolute configuration.
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