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For comparably efficient atom economic approaches to α,β- unsaturated esters that do not rely on aldehydes, see for example: (a) Heck-reaction, I.P. Beletskaya, and A.V. Cheprakov Chem. Rev. 100 2000 3009 3066
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28944437262
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28944449988
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2=Et) 10 mmol ca. 5 €; mono-ethyl malonate, potassium salt (7d ), 10 mmol ca. 2 €.
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85022955853
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28944445517
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in press.
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For a preliminray communication of our results, see: List, B.; Doehring, A.; Hechavarria Fonseca, M. T.; Wobser, K.; van Thienen, H.; Rios Torres, R.; Llamas Galilea, P., Adv. Synth. Catal. 2005, in press.
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Llamas Galilea, P.7
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33947551269
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For mechanistic discussions of this observation, see: E.J. Corey J. Am. Chem. Soc. 74 1952 5897 5905
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84985644483
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In one report DMAP has been used as a catalyst for the reaction of malonic acid half esters with α,β-unsaturated aldehydes at elevated temperature in pyridine to give the corresponding α,β,γ, δ-unsaturated esters. See: J. Rodriguez, and B. Waegell Synthesis 1988 534 535
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13644256524
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List, B.1
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0000129803
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In our experience, acetals of aromatic aldehydes can be transformed into the α,β-unsaturated ester under the slightly acidic reaction conditions. Also see: J. Klein, and E.D. Bergmann J. Am. Chem. Soc. 79 1957 3452 3454
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'Process for the production of olefins from carbonyl compounds' (Studiengesellschaft Kohle mbH), Patent pending.
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19744363827
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For recent studies on the use of malonic acid half thioesters in asymmetric catalysis, see: D. Magdziak, G. Lalic, H.M. Lee, K.C. Fortner, A.D. Aloise, and M.D. Shair J. Am. Chem. Soc. 127 2005 7284 7285
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28944431710
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note
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In selected cases (see Tables), piperidine (10 mol%) was added as co-catalyst (at 10°C) to reduce the reaction times.
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