CSIRO Publishing blank image blank image blank image blank imageBooksblank image blank image blank image blank imageJournalsblank image blank image blank image blank imageAbout Usblank image blank image blank image blank imageShopping Cartblank image blank image blank image You are here: Journals > Australian Journal of Chemistry   
Australian Journal of Chemistry
Journal Banner
  An international journal for chemical science
blank image Search
blank image blank image
blank image
  Advanced Search

Journal Home
About the Journal
Editorial Structure
For Advertisers
Online Early
Current Issue
Just Accepted
All Issues
Virtual Issues
Special Issues
Research Fronts
Sample Issue
For Authors
General Information
Submit Article
Author Instructions
Open Access
For Referees
Referee Guidelines
Review an Article
For Subscribers
Subscription Prices
Customer Service
Print Publication Dates
Library Recommendation

blue arrow e-Alerts
blank image
Subscribe to our Email Alert or RSS feeds for the latest journal papers.

red arrow Connect with us
blank image
facebook twitter logo LinkedIn

Affiliated with RACI

Royal Australian Chemical Institute
Royal Australian
Chemical Institute


Article << Previous     |     Next >>   Contents Vol 64(4)

Fluoroazaindolines by an Uncommon Radical ipso-Substitution of a C-F Bond

Yann Laot A, Laurent Petit A, Ngoc Diem My Tran A and Samir Z. Zard A B

A Laboratoire de Synthèse Organique, UMR 7652 CNRS/Ecole Polytechnique, 91128 Palaiseau, France.
B Corresponding author. Email: zard@poly.polytechnique.fr

Australian Journal of Chemistry 64(4) 416-425 http://dx.doi.org/10.1071/CH10422
Submitted: 22 November 2010  Accepted: 27 January 2011   Published: 18 April 2011

PDF (836 KB) $25
 Supplementary Material
 Export Citation

Trifluoroazaindoline derivatives are prepared using the first synthetically useful radical ipso-substitution of a fluorine atom. The initial procedure has been improved to allow the gram scale synthesis of these building blocks, which can be regioselectively substituted by nucleophiles under mild conditions to rapidly access a library of new molecules. Oxidation to the corresponding fluoroazaindole core has also been accomplished.


[1]  (a) For reviews on xanthate chemistry, see: B. Quiclet-Sire, S. Z. Zard, Top. Curr. Chem. 2006, 264, 201. 10.1007/128_029
      (b) B. Quiclet-Sire, S. Z. Zard, Chemistry 2006, 12, 6002.
         | CrossRef |
         (c) (c) S. Z. Zard, in Radical in Organic Chemistry (Eds P. Renaud, M. P. Sibi) 2001, Vol. 1, pp. 90–108 (Wiley-VCH, Weinheim).
      (d) B. Quiclet-Sire, S. Z. Zard, Phosphorus Sulfur Silicon 1999, 153, 137.
         | CrossRef |
      (e) B. Quiclet-Sire, S. Z. Zard, J. Chin. Chem. Soc. 1999, 46, 139.
      (f) S. Z. Zard, Angew. Chem. Int. Ed. Engl. 1997, 36, 672.
         | CrossRef |

[2]  E. Bacqué, M. El Qacemi, S. Z. Zard, Org. Lett. 2004, 6, 3671.
         | CrossRef | PubMed |

[3]  (a) M. El Qacemi, L. Ricard, S. Z. Zard, Chem. Comm. 2006, , 4422.
         | CrossRef | CAS |
      (b) Y. Laot, L. Petit, S. Z. Zard, Chem. Commun. (Camb.) 2010, 46, 5784.
         | CrossRef |

[4]  We wish to acknowledge in this respect our collaboration on the theoretical aspects with Dr Michelle Coote at the Australian National University.

[5]  This work was reported in a preliminary communication: Y. Laot, L. Petit, S. Z. Zard, Org. Lett. 2010, 12, 3426. 10.1021/OL101240F

[6]  (a) Pentafluoropyridine usually reacts with amines first at the 4-position then at the 2-position. See for example: C. A. Hargreaves, G. Sanford, R. Slater, D. S. Yufit, J. A. K. Howard, A. Vong, Tetrahedron 2007, 63, 5204. 10.1016/J.TET.2007.03.164
      (b) H. Amii, K. Uneyama, Chem. Rev. 2009, 109, 2119.
         | CrossRef |

[7]  (a) G. M. Brooke, J. Fluor. Chem. 1997, 86, 1.
         | CrossRef |
      (b) L. S. Kobrina, J. Fluor. Chem. 1989, 42, 301.
         | CrossRef |
      (c) P. A. Claret, G. H. Williams, J. Coulson, J. Chem. Soc. C 1968, , 341.
         | CrossRef |

[8]  (a) J. A. Struss, M. Sadeghipour, J. M. Tanko, Tetrahedron Lett. 2009, 50, 2119.
         | CrossRef | CAS |
      (b) M. L. Maddess, E. Mainetti, Y. Harrak, C. Brancour, P. Devin, A.-L. Dhimane, L. Fensterbank, M. Malacria, Chem. Commun. (Camb.) 2007, , 936.
         | CrossRef |
      (c) S. Kim, N. Kim, W.-J. Chung, C. H. Cho, Synlett 2001, , 937.
         | CrossRef |
      (d) J. M. Tanko, M. Sadeghipour, Angew. Chem. Int. Ed. 1999, 38, 159.
         | CrossRef |
      (e) C. C. Huval, D. A. Singleton, Tetrahedron Lett. 1993, 34, 3041.
         | CrossRef |
      (f) G. A. Kraus, B. Andersh, Q. Su, J. Shi, Tetrahedron Lett. 1993, 34, 1741.
         | CrossRef |
      (g) S. Knapp, F. S. Gibson, Y. H. Choe, Tetrahedron Lett. 1990, 31, 5397.
         | CrossRef |
      (h) G. F. Meijs, E. Rizzardo, S. H. Tang, Polym. Bull. 1990, 24, 501.
         | CrossRef |

[9]  For a review, see: J. A. Walton, A. Studer, Acc. Chem. Res. 2005, 38, 794. 10.1021/AR050089J

[10]  (a) A. L. J. Beckwith, D. Crich, P. J. Duggan, Q. Yao, Chem. Rev. 1997, 97, 3273.
         | CrossRef | CAS | PubMed |
      (b) D. Crich, F. Brebion, D.-H. Suk, Top. Curr. Chem. 2006, 263, 1.
         | CrossRef |

[11]  L. C. T. Shoute, J. P. Mittal, J. Phys. Chem. 1993, 97, 379.
         | CrossRef | CAS |

[12]  For an example of the use of high temperature to force a difficult cyclization on an aromatic ring, see: B. Quiclet-Sire, S. Z. Zard, Chem. Commun. (Camb.) 2002, 2306. 10.1039/B207649G

[13]  (a) The use of ring-fused trifluoropyridine systems in further synthetic transformations has recently been described. See for example: G. Sandford, R. Slater, D. S. Yufit, J. A. K. Howard, A. Vong, J. Org. Chem. 2005, 70, 7208. 10.1021/JO0508696
      (b) M. W. Cartwright, L. Convery, T. Kraynck, G. Sandford, D. S. Yufit, J. A. K. Howard, J. A. Christopher, D. D. Miller, Tetrahedron 2010, 66, 519.
         | CrossRef |

[14]  (a) For some recent references, see: M. Jeanty, J. Blu, F. Suzenet, G. Guillaumet, Org. Lett. 2009, 11, 5142 10.1021/OL902139R
      (b) M. P. Huestis, K. Fagnou, Org. Lett. 2009, 11, 1357.
         | CrossRef |
      (c) A. Echalier, K. Bettayeb, Y. Ferandin, O. Lozach, M. Clément, A. Valette, F. Liger, B. Marquet, J. P. Morris, J. A. Endicott, B. Joseph, L. Meijer, J. Med. Chem. 2008, 51, 737.
         | CrossRef |
      (d) M. Jeanty, F. Suzenet, G. Guillaumet, J. Org. Chem. 2008, 73, 7390.
         | CrossRef |
      (e) P. Wipf, J. P. Maciejewski, Org. Lett. 2008, 10, 4383.
         | CrossRef |
      (f) Y. Ma, S. Breslin, I. Keresztes, E. Lobkovsky, D. B. Collum, J. Org. Chem. 2008, 73, 9610.
         | CrossRef |
      (g) Y.-Q. Fang, Y. Yuen, M. Lautens, J. Org. Chem. 2007, 72, 5152.
         | CrossRef |

[15]  (a) F. Popowycz, S. Routier, B. Joseph, J.-Y. Mérour, Tetrahedron 2007, 63, 1031.
         | CrossRef | CAS |
      (b) F. Popowycz, B. Joseph, J. Y. Mérour, Tetrahedron 2007, 63, 8689.
         | CrossRef |
      (c) J. J. Song, J. T. Reeves, F. Gallou, Z. Tan, N. K. Yee, C. H. Senanayake, Chem. Soc. Rev. 2007, 36, 1120.
         | CrossRef |

[16]  (a) V. A. Azimov, N. N. Bychikhina, A. I. Polezhaeva, M. D. Mashkovskii, L. N. Yakhontov, Pharm. Chem. J. 1980, 14, 308.
      (b) T. Hara, K. Mori, T. Mizugaki, K. Ebitani, K. Kaneda, Tetrahedron Lett. 2003, 44, 6207.
         | CrossRef |
      (c) A. L. Borror, E. Chinoporos, M. P. Filosa, S. R. Herchen, S. P. Petersen, C. A. Stern, J. Org. Chem. 1988, 53, 2047.
         | CrossRef |
      (d) J. A. Weightgenant, I. Katsuyama, M. A. Bigi, S. J. Corden, J. T. Markiewicz, A. P. R. Zabell, K. T. Homan, O. Wiest, C. V. Stauffacher, P. Helquist, Heterocycles 2006, 70, 599.
         | CrossRef |
      (e) U. Tilstam, M. Harre, T. Heckrodt, H. Weinmann, Tetrahedron Lett. 2001, 42, 5385.
         | CrossRef |

[17]  K. C. Nicolaou, C. J. N. Mathison, T. Montagnon, J. Am. Chem. Soc. 2004, 126, 5192 and references therein. 10.1021/JA0400382

[18]  R. Poe, K. Schnapp, M. J. T. Young, J. Grayzar, M. S. Platz, J. Am. Chem. Soc. 1992, 114, 5054.
         | CrossRef | CAS |

[19]  F. H. Compounds, Synthesis, Chemistry and Applications (Ed. V. A. Petrov) 2009 (J. Wiley & Sons, Inc.: Hoboken, NJ).

Subscriber Login


Legal & Privacy | Contact Us | Help


© CSIRO 1996-2016