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note
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2-symmetric amines were expected (1d and 1e). Although both dienes were easily prepared using the general procedure outlined in the text (59% and 79% yields, respectively), they did not give superior results in the cycloaddition reactions compared to those obtained with diene 3c, and thus they were not investigated as thoroughly. Diene 3d was prepared from the commercially available secondary amine 1d. It gave a messy reaction with methacrolein and an unpromising 30:24:29:17 mixture of four diastereomers with methyl acrylate. The mannitol-derived compound 1e, was also synthesized and examined briefly. However, diene 3e, derived from this amine, was less reactive than the other dienes, and the yields and ee's were no better than those obtained with diene 3c. The following results were obtained for the cycloaddition/reduction/hydrolysis sequence using diene 3e: (a) methacrolein, 33% yield, 67% ee; (b) methyl acrylate, 63% yield, 75% ee; (c) diethyl fumarate, 57% yield, 85% ee. (matrix presented)
-
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(a) SMP was purchased from Aldrich Chemical Co. (b) RDMP was purchsed from Acros Organics.
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note
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The assignment of the relative stereochemistry was made based on the multiplicity of the silyl enol ether proton. In the case of the endo-isomer this proton is observed as a doublet with a J value of 5-6 Hz, due to the coupling to the vicinal proton adjacent to the amino group. The similar resonance corresponding to the exo-diastereomer is usually displayed as a triplet with a very small coupling constant of 1-2 Hz.
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