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16
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26044460689
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note
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3OD) δ 1.81 (1H, dd, J = 13.5, 11.7 Hz, H-2β), 2.19 (1H, dd, J = 13.5, 5.0 Hz, H-2α), 3.45 (1H, dd, J = 9.6, 3.0 Hz, H-4), 3.78 (3H, s, COOMe), 3.98 (1H, ddd, J = 11.7, 9.6, 5.0 Hz, H-3), 4.10 (1H, dd, J = 3.0, 2.8 Hz, H-5), 4.49 (1H, d, J = 2.8 Hz, H-6). Observation of the NOESY cross peaks H-6/H-4, H-6/H-2β, and H-4/H-2β in 19 supported the conformation shown below. These results elucidated the stereochemistry of C-6 in 5 or C-5 in 6. (Chemical Equation Presented) 6 19 Figure 2.
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18
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26044447558
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note
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Observing the NOESY cross peaks H-6/H-4, H-6/H-2β, and H-4/H-2β in 10 as in 19 suggested the configuration at C-4 as shown in Scheme 1.
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20
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26044444265
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note
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Observation of the NOESY cross peak between H-4 and H-6 in 13 suggested that H-4 and H-6 had the cis-configuration. And as described in text part, observation of the cross peaks between the proton signal of one of acetonide-methyl groups and H-4 or H-5 in the NOESY spectra of 15, which was derived from 13 via 1, implied that H-4 and H-5 had cis-configuration in 13. Therefore the possibility of epimerization at C-4 or C-6 during transformation from 12 to 13 was denied.
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22
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26044456612
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note
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+, 223.0372; Found, 223.0360.
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23
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26044445103
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note
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+, 223.0372; Found, 223.0379.
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