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1
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84920310311
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note
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Except where indicated, all new compounds were prepared as racemates. The stereochemistry illustrated for all new compounds was chosen based on the absolute stereochemistry of 12a as defined by X-ray structure analysis of its p-bromobenzyl ether.
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3
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We also attempted to prepare the C-4 acetoxy product by acylation of the C-7 TIPS-protected phenol 29. In this case fluoride deprotection afforded only 10a and its trans epimer 10b. This is consistent with the proposed rapid formation of a quinone methide when a good C-4 leaving group is present and capture with water upon workup. The same result was observed when we attempted to introduce a C-4 benzoyl group.
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The trans isomer 36b was not obtained 100% pure. Stereochemical assignments for 36a and 36b followed from the NMR decoupling experiments below. (Left) Irradiation at 5.31 ppm results in loss of the 1.6-Hz coupling to the proton at 0.96 ppm. (Right) Irradiation at 4.32 ppm results in loss of the 1.3-Hz coupling to the proton at 5.06 ppm, loss of the 3.9-Hz coupling to the proton at 1,08 ppm, and loss of the 7.6-Hz coupling to proton at 0.99 ppm.
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