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26844448806
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note
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The presence of the endo-isomer of 17 as the minor component in the mixture of reaction products was shown by NMR spectroscopy and mass spectrometry (see Supporting Information). 2-TST addition to ketone 16 appears to give a "mismatched" reaction, with the exo-addition product formed in modest excess. In contrast, the corresponding addition to diastereomeric ketone 2 appears to be "matched" with respect to generation of the desired endo-adduct required for aceric acid synthesis.
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26844455030
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note
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NOEs for compounds 6, 15, 24, and 25 were in the 2-3% range. Details of the observed NOEs, which were obtained for these compounds upon selective irradiation of the signals corresponding to H-1, H-2, H-3, H-4, and H-3′, are summarized in Supporting Information.
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