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note
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The stereoselective synthesis of α-amino-β-hydroxy acids is an intensive research field, since these acids are building blocks of numerous peptide-based natural products including the vancomycin antibiotics; see references in ref 7.
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30
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0346351277
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note
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4 to Y are much higher in energies than their corresponding Diels-Alder TSs (see Figure S12 in the Supporting Information).
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48
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298 (see Supporting Information for the energies and structures of DA TS 9 and adduct 10).
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55
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0346981155
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note
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An interesting feature worthy of note is that the cis-3-thiazoline 4 is more stable than trans-3-thiazoline 8 by about 0.4 kcal/mol. So is the 3-oxazoline which has the cis-3-oxazoline being more stable than trans-3-oxazoline by about 0.4 kcal/mol, too. The reason for this cis preference is probably the electronic attraction between the two groups.
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56
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0348241962
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note
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3.5a This path can be easily excluded, owing to the high activation energy of 30.2 kcal/mol needed to generate the ylide 16 (see Figure S7 in Supporting Information). In terms of free energy, the pseudopericyclic TS 15 is still higher than the rate-determining TS 1 in the manifold A by about 8 kcal/mol. Furthermore, the ylide is a species lying higher in energy than the reactants by around 20.6 kcal/mol, suggesting that the backward ring-closing reaction converting ylide to oxazole is more efficient.
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59
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0348241963
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1 bond.
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