Synthesis 2019; 51(12): 2548-2552
DOI: 10.1055/s-0037-1611532
paper
© Georg Thieme Verlag Stuttgart · New York

Formation of Aryl [1-Cyano-4-(dialkylamino)butadienyl] Ketones from Pyridines

Hyo Jin Gim
,
Department of Chemistry and Biochemistry, University of California Los Angeles, Los Angeles, CA 90095, USA   Email: jung@chem.ucla.edu
› Author Affiliations
We thank the California Institute for Regenerative Medicine (CIRM) program at UCLA for support.
Further Information

Publication History

Received: 07 March 2019

Accepted after revision: 10 April 2019

Publication Date:
02 May 2019 (online)


Abstract

Treatment of 2-chloropyridine with LDA and the Weinreb amide of benzoic acid afforded three unusual products, namely N-methylbenzamide, 2-chloropyridine-3-methanol, and the ring-opened addition product. This same final product could also be obtained from 2-chloro-3-benzoylpyridine on treatment with LDA. Mechanistic insight for the formation of these products is provided.

Supporting Information

 
  • References

  • 1 Zhang, Y.; Roos, M.; Himburg, H.; Termini, C. M.; Quarmyne, M.; Yan, X.; Zhao, L.; Kan, J.; Fang, T.; Li, M.; Pohl, K.; Diers, E.; Gim, H. J.; Damoiseaux, R.; Whitelegge, J.; McBride, W.; Jung, M. E.; Chute, J. P. Nat. Commun. manuscript submitted.
    • 2a Marquise N, Nguyen TT, Chevallier F, Picot L, Thiery V, Lozach O, Bach S, Ruchaud S, Mongin F. Synlett 2015; 26: 2811
    • 2b Marquise N, Harford PJ, Chevallier F, Roisnel T, Dorcet V, Gagez A.-L, Sable S, Picot L, Thiery V, Wheatley AE. H, Gros PC, Mongin F. Tetrahedron 2013; 69: 10123
  • 3 Gribble GW, Saulnier MG. Tetrahedron Lett. 1980; 21: 4137
  • 4 Weinreb SM, Nahm S. Tetrahedron Lett. 1981; 22: 3815
    • 5a Marsais F, Laperdrix B, Güngör T, Mallet M, Quéguiner G. J. Chem. Res., Synop. 1982; 278
    • 5b Marsais F, Laperdrix B, Güngör T, Mallet M, Quéguiner G. J. Chem. Res., Miniprint 1982; 2863
    • 5c Newkome GR, Sauer JD, Staires SK. J. Org. Chem. 1977; 42: 3524
    • 5d Utimoto K, Sakai N, Nozaki H. J. Am. Chem. Soc. 1974; 96: 5601
    • 5e Vander Lans HM. N, Den Hertog JJ, Van Veldhuizen A. Tetrahedron Lett. 1971; 12: 1875
  • 6 Kowalski C, Creary X, Rollin AJ, Burke AC. J. Org. Chem. 1978; 43: 2601

    • The formation of this anion is precedented in the literature:
    • 7a Hedidi M, Maillard J, Erb W, Lassagne F, Halauko YS, Ivashkevich OA, Matulis VE, Roisnel T, Dorcet V, Hamze M, Fajloun Z, Baratte B, Ruchard S, Bach S, Bentabed-Ababsa G, Mongin F. Eur. J. Org. Chem. 2017; 5903
    • 7b Hedidi M, Erb W, Lassagne F, Halauko YS, Ivashkevich OA, Matulis VE, Roisnel T, Bentabed-Ababsa G, Mongin F. RSC Adv. 2016; 6: 63185
    • 8a CCDC 1900152 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Centre via www.ccdc.cam.ac.uk/getstructures.
    • 8b We thank Dr. Saeed Khan for carrying out the single crystal X-ray determination.