Tether-controlled cycloadditions for the asymmetric synthesis of decalins: increased selectivity in acetonitrile solvent.
[reaction: see text] The beneficial influence of cis-isopropylidene acetal tether control groups, to facilitate the asymmetric synthesis of substituted decalins by intramolecular Diels-Alder reactions, is described. Compared to trans-acetonides, these cases proceed under milder conditions to afford the cis-fused adducts from an endo transition state. An unusual acetonitrile solvent effect exerts a dramatic influence on the diastereoselectivity. This strategy leads to the chiral nonracemic bicyclo[4.4.0]decane core of diverse natural products.
Melekhov
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Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario, Canada K1N 6N5.
Forgione
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Legoupy
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D000097:Acetonitriles / Q000737:chemistry*; D009281:Naphthalenes / Q000138:chemical synthesis*; D012997:Solvents; D013237:Stereoisomerism
D000097:Acetonitriles; D009281:Naphthalenes; D012997:Solvents; C007229:decalin; C032159:acetonitrile