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2 afforded comparable reactivity as far as reaction rates and stereoselectivity but with significantly lower chemical yields (59%).
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2 afforded comparable reactivity as far as reaction rates and stereoselectivity but with significantly lower chemical yields (59%).
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0034742945
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When the unprotected substrate (S)-l was used, complex reaction mixtures were obtained where complete substrate disappearance and no significant amount of iodocyclization products were detected. Reactions between iodine and and amines have been reported to afford N-iodination, formation of molecular complexes, and in some cases, unusual oxidation processes, and therefore N-protection is required. See: Jones, A. D.; Knight, D. W.; Hibbs, D. E. J. Chem. Soc., Perkin Trans. 1 2001, 1182-1203 and refs therein.
-
When the unprotected substrate (S)-l was used, complex reaction mixtures were obtained where complete substrate disappearance and no significant amount of iodocyclization products were detected. Reactions between iodine and and amines have been reported to afford N-iodination, formation of molecular complexes, and in some cases, unusual oxidation processes, and therefore N-protection is required. See: Jones, A. D.; Knight, D. W.; Hibbs, D. E. J. Chem. Soc., Perkin Trans. 1 2001, 1182-1203 and refs therein.
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2 appears as an ABX system at 2.42 and 2.71 ppm in 4a, whereas in anti-4b it is at 1.96 and 3.12 ppm, respectively.
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2 appears as an ABX system at 2.42 and 2.71 ppm in 4a, whereas in anti-4b it is at 1.96 and 3.12 ppm, respectively.
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34250838336
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Although the diastereomeric mixtures 4a/4b and 6a/6b are separable through radial chromatography, the isomers 5a/5b remain unseparable
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Although the diastereomeric mixtures 4a/4b and 6a/6b are separable through radial chromatography, the isomers 5a/5b remain unseparable.
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46
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34250903274
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Examples of intramolecular cyclic carbamate formation with good stereoselectivities have been reported in the iodocyclization of a few acyclic homoallyl-ß-amino esters (carbamates vs δ-lactones, ref 17) and in one case on the bromocyclization of a bicyclic allyl α-amino ester where, for steric reasons, only the C=O carbamate could give the nucleophilic attack ref 18
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Examples of intramolecular cyclic carbamate formation with good stereoselectivities have been reported in the iodocyclization of a few acyclic homoallyl-ß-amino esters (carbamates vs δ-lactones) (ref 17) and in one case on the bromocyclization of a bicyclic allyl α-amino ester where, for steric reasons, only the C=O carbamate could give the nucleophilic attack (ref 18).
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34250811118
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Crystal Data for 7b: C14H16INO4, Mw, 389.18, T, 293(2) K, l, 0.71073 Å, orthorhombic, space group P212121, a, 6.725 Å, b, 13.858 Å, c, 16.061 Å, V, 1496.7 Å3, Z, 4, D c, 1.727 g/cm3, F(000, 768, crystal size 0.5 × 0.5 × 0.5 mm3, 24 277 reflections measured, 4577 independent reflections (Rint, 0.0206, the final wR(F2) was 0.1534 (all data) and final R was 0.0536 for 3704 unique data [I > 2s(I, The crystal structure of (4S,6R)-7b has been deposited at the Cambridge Crystallographic Data Centre CCDC 635632
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2) was 0.1534 (all data) and final R was 0.0536 for 3704 unique data [I > 2s(I)], The crystal structure of (4S,6R)-7b has been deposited at the Cambridge Crystallographic Data Centre (CCDC 635632).
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