CC BY-ND-NC 4.0 · Synthesis 2019; 51(05): 1135-1138
DOI: 10.1055/s-0037-1611650
feature
Copyright with the author

A Scalable, One-Pot Synthesis of 1,2,3,4,5-Pentacarbomethoxycyclopentadiene

M. Alex Radtke
a   Department of Chemistry, Columbia University, 3000 Broadway, New York, NY 10027, USA
,
Caroline C. Dudley
b   Department of Chemistry and Chemical Biology, Cornell University, 259 East Ave, Ithaca, NY 14850, USA   Email: Tristan.lambert@cornell.edu
,
Jacob M. O’Leary
b   Department of Chemistry and Chemical Biology, Cornell University, 259 East Ave, Ithaca, NY 14850, USA   Email: Tristan.lambert@cornell.edu
,
Tristan H. Lambert  *
a   Department of Chemistry, Columbia University, 3000 Broadway, New York, NY 10027, USA
b   Department of Chemistry and Chemical Biology, Cornell University, 259 East Ave, Ithaca, NY 14850, USA   Email: Tristan.lambert@cornell.edu
› Author AffiliationsThis work is supported by the NIH (R35 GM127135). This work made use of the Cornell University NMR Facility, which is supported, in part, by the NSF through MRI award CHE-1531632.
Further Information

Publication History

Received: 07 December 2018

Accepted: 14 December 2018

Publication Date:
22 January 2019 (online)

   Permissions and Reprints All articles of this category


Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

Abstract

1,2,3,4,5-Pentacarbomethoxycyclopentadiene (PCCP) is a strong organic acid and a precursor to useful organocatalysts, including chiral Brønsted acids and silicon-based Lewis acids. The synthetic route to PCCP, first reported in 1942, is inconvenient for a number of reasons. The two-step synthesis requires the purification of intermediates from intractable side-products, high reaction temperatures, and extensive labor (3 days). We have developed an improved procedure that delivers PCCP efficiently in 24 hours in one pot at ambient temperature and without isolation.

Key words

Brønsted acid - PCCP - cyclopentadiene - dimethyl malonate - dimethyl acetylenedicarboxylate
 

  • References

    • 1a Richardson C, Reed C. Chem. Commun. 2004; 706
      PubMed
    • 1b Cookson RC, Hudec J, Whitear BR. D. Proc. Chem. Soc. 1961; 117
    • 2a Diels O. Ber. Dtsch. Chem. Ges. 1942; 75: 1452
      Crossref
    • 2b Diels O, Kock U. Justus Liebigs Ann. Chem. 1944; 556: 38
      Crossref
    • 3a Gheewala CD, Collins BE, Lambert TH. Science 2016; 351: 961
      CrossrefPubMed
    • 3b Gheewala CD, Hirschi JS, Lee W, Paley DW, Vetticatt MJ, Lambert TH. J. Am. Chem. Soc. 2018; 140: 3523
      CrossrefPubMed
    • 3c Radtke MA, Lambert TH. Chem. Sci. 2018; 9: 6406
      CrossrefPubMed
  • 4 Gheewala CD, Radtke MA, Hui J, Hon AB, Lambert TH. Org. Lett. 2017; 19: 4227
    CrossrefPubMed
  • 5 Bruce MI, White AH. Aust. J. Chem. 1990; 43: 949
    Crossref
  • 6 Le Goff E, LaCount RB. J. Org. Chem. 1964; 29: 423
    Crossref
  • 7 Salikov RF, Trainov KP, Platonov DN, Belyy AY, Tomilov YV. Eur. J. Org. Chem. 2018; 5065
    • 8a Yuan C, Li J, Li P. ACS Omega 2018; 6: 6820
    • 8b Qiao X, El-Shahat M, Ullah B, Bao Z, Xing H, Xiao L, Ren Q, Zhang Z. Tetrahedron Lett. 2017; 58: 2050
      Crossref
    • 8c Sui Y, Cui P, Liu S, Zhou Y, Du P, Zhou H. Eur. J. Org. Chem. 2018; 215
    • 8d Zhao X, Xiao J, Tang W. Synthesis 2017; 49: 3157
      Article in Thieme Connect