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Volumn 62, Issue 2-3, 2006, Pages 476-482

A practical, efficient, and atom economic alternative to the Wittig and Horner-Wadsworth-Emmons reactions for the synthesis of (E)-α,β- unsaturated esters from aldehydes

Author keywords

, Unsaturated esters; (E) Stereoselectivity; DMAP catalysis; Doebner Knoevenagel reaction

Indexed keywords

ALDEHYDE DERIVATIVE; CINNAMIC ACID DERIVATIVE; ESTER DERIVATIVE; MALONIC ACID;

EID: 28944451360     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2005.09.081     Document Type: Article
Times cited : (68)

References (52)
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    • For selected alternative processes, see: (a) Claisen-Schmidt-type condensation of aromatic aldehydes: M. Hatsuda, T. Kuroda, and M. Seki Synth. Commun. 33 2003 427 432
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    • (b) From ethyl diazoacetate and stoichiometric phosphine via transition metal catalysis: W.A. Hermann, and M. Wang Angew. Chem. 103 1991 1709 1711
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    • (h) From ethyl bromoacetate in the presence of a Te-catalyst, potassium carbonate, sodium bisulfite, and triphenyl phosphite: Z.-Z. Huang, S. Ye, W. Sia, and Y. Tang Chem. Commun. 15 2001 1384 1385
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  • 18
    • 0034249671 scopus 로고    scopus 로고
    • 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
    • (2000) Chem. Rev. , vol.100 , pp. 3009-3066
    • Beletskaya, I.P.1    Cheprakov, A.V.2
  • 20
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    • (BASF AG, Germany). Eur. Pat. Appl. EP 6385807, 1995, p 7, CAN 123:9689.
    • 2), see: Process for the manufacture of triphenyl phosphine. Hermeling, D.; Bassler, P.; Hammes, P.; Hugo, R.; Lechtken, P.; Siegel, H., (BASF AG, Germany). Eur. Pat. Appl. EP 6385807, 1995, p 7, CAN 123:9689.
    • Hermeling, D.1    Bassler, P.2    Hammes, P.3    Hugo, R.4    Lechtken, P.5    Siegel, H.6
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    • (a) For aromatic aldehydes, see: A. Galat J. Am. Chem. Soc. 68 1946 376 377
    • (1946) J. Am. Chem. Soc. , vol.68 , pp. 376-377
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  • 25
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    • note
    • 2=Et) 10 mmol ca. 5 €; mono-ethyl malonate, potassium salt (7d ), 10 mmol ca. 2 €.
  • 30
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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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    • Corey, E.J.1
  • 32
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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
    • (1988) Synthesis , pp. 534-535
    • Rodriguez, J.1    Waegell, B.2
  • 34
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    • R. Mahrwald Wiley-VCH Weinhein, Germany
    • Also see: B. List R. Mahrwald Modern Aldol Reactions Vol. 1 2004 Wiley-VCH Weinhein, Germany 161 200
    • (2004) Modern Aldol Reactions , vol.1 , pp. 161-200
    • List, B.1
  • 35
    • 0000129803 scopus 로고
    • 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
    • (1957) J. Am. Chem. Soc. , vol.79 , pp. 3452-3454
    • Klein, J.1    Bergmann, E.D.2
  • 37
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    • 'Process for the production of olefins from carbonyl compounds' (Studiengesellschaft Kohle mbH), Patent pending.
    • 'Process for the production of olefins from carbonyl compounds' (Studiengesellschaft Kohle mbH), Patent pending.
  • 39
    • 28944431710 scopus 로고    scopus 로고
    • note
    • In selected cases (see Tables), piperidine (10 mol%) was added as co-catalyst (at 10°C) to reduce the reaction times.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.