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(a) Enders, D.; Niemeier, O.; Balensiefer, T. Angew. Chem. 2006, 118, 1491-1495;
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For the proline-catalyzed synthesis of dihydrobenzofuranols, see
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For the proline-catalyzed synthesis of dihydrobenzofuranols, see: Enders, D.; Niemeier, O.; Straver, L. Synlett 2006, 3399-3402.
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For a review on biomimetic natural product syntheses via polyolefin carbocyclizations, see
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For a review on biomimetic natural product syntheses via polyolefin carbocyclizations, see: Yoder, R. A.; Johnston, J. N. Chem. Rev. 2005, 105, 4730-4756.
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For a recent review on organocatalytic domino reactions, see
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(b) For a recent review on organocatalytic domino reactions, see: Enders, D.; Grondal, C.; Hüttl, M. R. M. Angew. Chem. 2007, 119, 1590-1601;
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For a perspective on enantioselective cascade catalysis, see: e
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(c) For a perspective on enantioselective cascade catalysis, see: (e) Walji, A. M.; MacMillan, D. W. C. Synlett 2007, 1477-1489.
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We presume that the catalyst preferentially reacts with the aliphatic aldehyde 109, not the α,β-unsaturated aldehyde 111, until all of the aliphatic aldehyde 109 has been consumed in the first Michael addition with nitroalkene 110. In this case, the concentration of the iminium-ion activated α,β-unsaturated aldehyde 115 would be low at the beginning of the reaction further explaining the chemoselectivity of the first step.
-
We presume that the catalyst preferentially reacts with the aliphatic aldehyde 109, not the α,β-unsaturated aldehyde 111, until all of the aliphatic aldehyde 109 has been consumed in the first Michael addition with nitroalkene 110. In this case, the concentration of the iminium-ion activated α,β-unsaturated aldehyde 115 would be low at the beginning of the reaction further explaining the chemoselectivity of the first step.
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149
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