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85007644768
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The aldehyde 6, which bears the primary pivaloate, was prepared by the same route as previously described for the corresponding MOM ether in 62% overall yield.
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32
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85007653720
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note
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Stannane 7 is conveniently prepared by deprotonation of 3-methyl-3-buten-1-ol with two equivalents of Schlosser's base, quenching the resulting dianion with tributyltin iodide, and protection of the resultant alcohol (TBSCI, imidazole).
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85007624890
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Small-scale reactions permitted the chromatographic separation of homoallylic alcohol diastereomers for individual characterization. Preparative multigram reactions were conveniently carried forward to acetal 16, where the desired C37 isomer was easily purified by flash chromatography.
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13C NMR spectroscopic analysis.
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46
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85007638185
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Model studies had shown that individual diastereomericallylic alcoholswere cyclized under these conditions to afford the same tetrahydropyran product.
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85007643343
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