Download PDF
Synlett 2012; 23(16): 2389-2392
DOI: 10.1055/s-0032-1317155
letter
© Georg Thieme Verlag Stuttgart · New York

Palladium-Catalyzed Reduction of Acid Chlorides to Aldehydes with Hydrosilanes

Tetsuaki Fujihara
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan   Fax: +81(75)3832514   Email: ytsuji@scl.kyoto-u.ac.jp
,
Cong Cong
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan   Fax: +81(75)3832514   Email: ytsuji@scl.kyoto-u.ac.jp
,
Tomohiro Iwai
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan   Fax: +81(75)3832514   Email: ytsuji@scl.kyoto-u.ac.jp
,
Jun Terao
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan   Fax: +81(75)3832514   Email: ytsuji@scl.kyoto-u.ac.jp
,
Yasushi Tsuji*
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan   Fax: +81(75)3832514   Email: ytsuji@scl.kyoto-u.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 06 July 2012

Accepted after revision: 31 July 2012

Publication Date:
11 September 2012 (online)

    Permissions and Reprints All articles of this category


Abstract

An efficient synthesis of aldehydes from acid chlorides with hydrosilanes as a reducing agent in the presence of a palladium catalyst has been achieved. A simple mixture of commercially available Pd(dba)2 and Mes3P as a catalyst realized the reduction of various acid chlorides including aliphatic acid chlorides and α,β-­unsaturated acid chlorides to the corresponding aldehydes in good to high yields under mild reaction conditions.

Key words

acid chloride - aldehyde - hydrosilane - palladium - phosphine

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
  • Supporting Information
 

  • References and Notes

  • 1 Larock RC. Comprehensive Organic Transformation: A Guide to Functional Group Preparation. 2nd ed. Wiley-VCH; New York: 1999
    Google Scholar
    • 2a Rosenmund KW. Ber. Dtsch. Chem. Ges. 1918; 51: 585
      Crossref
    • 2b Mosettig E, Mozingo R. Org. React. 1948; 4: 362
    • 3a Brown HC, McFarlin RF. J. Am. Chem. Soc. 1956; 78: 252
      Crossref
    • 3b Brown HC, Krishnamurthy S. Tetrahedron 1979; 35: 567
      Crossref
    • 3c Cha JS, Brown HC. J. Org. Chem. 1993; 58: 4732
      Crossref
    • 4a Babler JH, Invergo BJ. Tetrahedron Lett. 1981; 22: 11
      Crossref
    • 4b Babler JH. Synth. Commun. 1982; 12: 839
      Crossref
    • 5a Four P, Guibe F. J. Org. Chem. 1981; 46: 4439
      Crossref
    • 5b Inoue K, Yasuda M, Shibata I, Baba A. Tetrahedron Lett. 2000; 41: 113
      Crossref
    • 5c Malanga C, Mannucci S, Lardicci L. Tetrahedron Lett. 1997; 38: 8093
      Crossref
    • 6a Ojima I In The Chemistry of Organic Silicon Compounds. Patai S, Rapport Z. Wiley; Chichester: 1989: 1479-1526
      CrossrefGoogle Scholar
    • 6b Modern Reduction Methods. Andersson PG, Munslow IJ. Wiley-VCH; Weinheim: 2008
      CrossrefGoogle Scholar
    • 7a Citron JD. J. Org. Chem. 1969; 34: 1977
      Crossref
    • 7b Dent SP, Eaborn C, Pidcock A. J. Chem. Soc., Chem. Commun. 1970; 1703
    • 7c Courtis B, Dent SP, Eaborn C, Pidcock A. J. Chem. Soc., Dalton Trans. 1975; 2460
    • 7d Dent SP, Eaborn C, Pidcock A. J. Chem. Soc., Dalton Trans. 1975; 2646
  • 8 Lee K, Maleczka RE. Jr. Org. Lett. 2006; 8: 1887
    Crossref
  • 9 Gutsulyak DV, Niknov GI. Adv. Synth. Catal. 2012; 354: 607
    Crossref
    • 10a Iwai T, Fujihara T, Terao J, Tsuji Y. J. Am. Chem. Soc. 2012; 134: 1268
    • 10b Iwai T, Fujihara T, Terao J, Tsuji Y. J. Am. Chem. Soc. 2009; 131: 6668
  • 11 Collman JP, Hegedus LS, Norton JR, Finke RG. Principles and Applications of Organotransition Metal Chemistry. University Science Books; Mill Valley / CA: 1987. Chap. 5
    Google Scholar
  • 12 Pd(dba)2 and Mes3P are commercially available from TCI and Aldrich
  • 13 Abbreviations: dba: dibenzylideneacetone, Mes3P: tris(2,4,6-trimethylphenyl)phosphine, (2-Tol)3P: tri-ortho-tolylphosphine, Cy3P: tricyclohexylphosphine, dppe: 1,3-bis(diphenylphosphino)ethane, dppf: 1,1′-bis(diphenylphosphino)ferrocene, rac-BINAP: 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl
  • 14 See Supporting Information for detail
    • 15a Franzen VV. Justus Liebigs Ann. Chem. 1956; 600: 109
      Crossref
    • 15b Burgstahler AW, Walker DE. Jr, Kuebrich JP, Schowen RL. J. Org. Chem. 1972; 37: 1272
      Crossref
    • 15c Seebach D, Erickson BW, Singh G. J. Org. Chem. 1966; 31: 4303
      Crossref
    • 15d Yamashita M, Miyoshi K, Nakazono Y, Suemitsu R. Bull. Chem. Soc. Jpn. 1982; 55: 1663
      Crossref
    • 15e Spletstoser JT, White JM, Georg GI. Tetrahedron Lett. 2004; 45: 2787
      Crossref
    • 16a Caseri W, Pregosin PS. J. Organomet. Chem. 1988; 356: 259
      Crossref
    • 16b Rendler S, Oestreich M, Butts CP, Lloyd-Jones GC. J. Am. Chem. Soc. 2007; 129: 502
      Crossref
  • 17 Catalytic reduction of 2-pyridinyl ester to aldehydes-d 1 with DSiMe2Ph was reported: Nakanishi J, Tatamidani H, Fukumoto Y, Chatani N. Synlett 2006; 869
    Article in Thieme Connect