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4544376317
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For the trans-configurated enol triflate the yield was determined over two steps since the diisobutylaluminum enolate was first trapped as the trimethylsilyl enol ether, which was cleaved with MeLi to form the more reactive lithium enolate.
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3 the product trans-4b was obtained in a comparable yield of 84%.
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4544283493
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note
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When the hexatrienes were heated at lower temperatures (150-160°C), the reaction required significantly longer times. For example, even after 12 h traces of the starting materials could be detected and, besides the desired products, several side products were formed.
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4544302200
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note
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1H NOESY NMR experiments in which interactions within the steroid analogue cis-6b between the protons of the methyl group at C13 and the proton at C14 as well as between the proton at C14 and the proton at C7 were detected. For the steroid trans-8b interactions between the methyl group at C13 and the proton at C8 could be observed, and also interactions between the proton at C7 and the proton at C8 as well as the proton at C14 and one proton at C15 were found.
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