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17644389626
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note
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After structural correction, the relative chemical shifts of the methyl and ten-butyl resonances exhibit the same trends for 19 and 28: 28-cis, 0.93 (s 9 H), 0.85 (d, 3 H, J = 7.1 Hz); 28-trans 0.97 (d, 3 H, J = 6.8 Hz), 0.84 (s, 9 H); 19-cis, 0.96 (s, 9 H), 0.91 (d, 3 H); 19-trans, 1.00 (d, 3 H, J = 7 HZ), 0.88 (s, 9 H). In the eis isomer, the methyl doublet resonates upfield from the tert-butyl singlet, while in the trans isomer the positions of these resonances are reversed.
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27
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17644384556
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note
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One minor product peak from this experiment did not match the GC peak for the very minor product 37 formed in the reduction of 18. This suggests either that the structure of 37 might be wrong or that 10a and 11a might be isomers at the ester bearing carbon rather than the ring fusion. Since the structures of all these minor product are tentative and since 37 was only formed in trace amounts, we decided not to pursue this issue further.
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17644416468
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note
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The alcohol shown below is formed by hydroboration of 40, and the stereoselectivity of the hydroboration (addition trans to the tert-butyl group) suggests that the Beckwith assumption of (kinetic) addition of hydrogen trans to the tert-butyl group is reasonable. To confirm the configuration of this alcohol, we converted it to the thionocarbonate followed by Barton-McCombie deoxygentation. This gave 28-cis as the only product. Further, the crystal structure of the derived 3,5-dinitrobezoate ester was also solved. See the Supporting Information for details. (Chemical Equation Presented)
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