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Vinylsilane 9 may be prepared in three steps from commercially available propargyl alcohol. See the Supporting Information.
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25
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23044466384
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note
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Lipase PS-D "Amano" I from Lot No. ILPSAY0352205K may be purchased from Amano Enzyme USA Co., Lomdard, IL 60148.
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26
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23044509425
-
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note
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The free alcohol of 10 was obtained in 94% yield (two steps from the racemic epoxide) and found to have 94-96% ee. Alcohol 11 was obtained in 89% yield and 94-97% ee.
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See the Supporting Information for experimental details.
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32
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23044472268
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note
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Minor amounts of side products of the reaction include homo-aldol coupling followed by dehydration and Peterson olefination to give the conjugated esters of 3 and 4.
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23044512856
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23044465940
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Enantiomeric excess (ee) analysis was preformed using chiral HPLC analysis with a CHIRALCEL OD column. See the Supporting Information.
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35
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2742569677
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It has been suggested that silicon prefers an axial orientation for both electronic and steric reasons but may still eliminate even without optimal orbital overlap. For a detailed discussion and relevant examples, see: Lambert, J. B. Tetrahedron 1990, 46, 2677.
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0034966749
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It is conceivable that an oxonia-Cope rearrangement could play a role in the stereochemical outcome of these reactions; however, no byproducts from this pathway were observed. For an example of oxonia-Cope rearrangements in allyl systems, see: Roush, W. R.; Dilley, G. J. Synlett 2001, SI, 955.
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For an example of oxonia-Cope rearrangement of ester-substituted oxycarbenium vinylsilanes to form dihydropyrans, see ref 2b.
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