A Facile Route to Symmetrical and Unsymmetrical Cycloalkeno[c]fused 2,2′-Bipyridine Ligands via Inverse Electron Demand Diels-Alder Reaction of 5,5′-bi-1,2,4-Triazines [1]

Abstract

A series of 6,6′-bisfunctionalized symmetrical cycloal­keno[c]fused 2,2′-bipyridines 4a-h or unsymmetrical cycloal­keno[c]fused 2,2′-bipyridines 6a-g is described. They were prepared by the Diels-Alder reaction of 3,3′-disubstituted 5,5′-bi-1,2,4-triazines 2a,b with cyclic enamines 3a-d. The regioselective reaction of 1-vinylimidazole (3e) with 2a leads to 5-(2-pyridyl)-1,2,4-triazine 9 which undergoes Diels-Alder reaction with cyclic enamines 3a-d to give unsymmetrical 2,2′-bipyridines 10a-d with one cycloalkene ring attached.

Diels-Alder reactions - annulenes - pyridines

References

1 Part 20 in 1,2,4-Triazines in Organic Synthesis. For part 19, see: Lipinska T. Tetrahedron Lett.  2002,  43:  9565 

2a Lehn J.-M. Supramolecular Chemistry, Concepts and Perspectives   VCH; Weinheim: 1995. 

2b Kaes C. Katz A. Hosseini MW. Chem. Rev.  2000,  100:  3553 

3 Schubert US. Eschbaumer C. Angew. Chem. Int. Ed.  2002,  41:  2892 

4a Pomeranc D. Heitz V. Chambron J.-C. Savage J.-P. J. Am. Chem. Soc.  2001,  123:  12215 

4b Demadis KD. Hartshorn CM. Meyer TJ. Chem. Rev.  2001,  101 

5a Keefe MH. Benkstein KD. Hupp JT. Coord. Chem. Rev.  2000,  205:  201 

5b Beer PD. Cadman J. Coord. Chem. Rev.  2000,  205:  131 

6 Pietraszkiewicz M. Karpiuk J. Pietraszkiewicz O. Spectrochim. Acta, Part A  1998,  54:  2229 ; and references cited therein

7 Pietraszkiewicz M. Comrehensive Supramolecular Chemistry, Luminescent Probes   Vol. 10:  Lehn J.-M. Kaes C. Katz A. Hosseini M. Pergamon; Oxford: 1996.  p.225 

8 Steel PJ. Adv. Heterocycl. Chem.  1997,  67:  1 

9a Ito K. Tabuchi S. Katsuki T. Synlett  1992,  575 

9b Ito K. Katsuki T. Tetrahedron Lett.  1993,  34:  2661 

9c Ito K. Yoshitake M. Katsuki T. Tetrahedron  1996,  52:  3905 

10a Kolp B. Abeln D. Stoeckli-Evans H. Von Zalewsky A. Eur. J. Inorg. Chem.  2001,  1207 

10b Von Zalewsky A. Mamula O. J. Chem. Soc. Dalton Trans.  2000,  219 ; and references cited therein

11 Varella JA. Castedo L. Maestro M. Mahia J. Saci C. Chem.-Eur. J.  2001,  7:  5203 

12 Bushby M. Moody CJ. Riddick DA. Waldron IR. J. Chem. Soc., Perkin Trans. 1  2001,  2183 

13 Rykowski A. Branowska D. Kielak J. Tetrahedron Lett.  2000,  41:  3657 

14 Rickborn B. In Organic Reactions   Vol. 53:  Paquette LA. John Wiley and Sons; New York: 1998.  p.493 

15 Neunhoeffer H. Lehmann B. Liebigs Ann. Chem.  1977,  1413 

16 Branowska D. Rykowski A. Synlett  2002,  1892 

17 Krass DK. Chen T.-K. Paudler WW. J. Heterocycl. Chem.  1973,  10:  343 

18 Boger DL. Weinreb SN. Hetero Diels-Alder Methodology in Organic Synthesis   Wasserman HH. Academic Press; New York: 1987. 

19a Baret P. Einhorn J. Gellon G. Pierre J.-L. Synthesis  1998,  431 

19b Mürner H. Von Zalewsky A. Stoeckli-Evans H. Inorg. Chem.  1996,  35:  3931 

20 Fletcher NC. J. Chem. Soc., Perkin Trans. 1  2002,  1831 

21a Barlow MG. Haszeldine RN. Simpkin DJ. J. Chem. Soc., Chem. Commun.  1979,  658 

21b Sagi M. Amano M. Konno S. Yamanaka H. Heterocycles  1989,  29:  2249 

21c Pabst GR. Pfüller OC. Sauer J. Tetrahedron  1999,  55:  5047 

21d Pabst GR. Sauer J. Tetrahedron  1999,  55:  5067 

21e Neunhoeffer H. In Comprehensive Heterocyclic Chemistry II, 1,2,4-Triazines and their Benzo Derivatives   Vol. 5:  Katritzky AR. Rees CW. Scriven EF. Pergamon Press; NY: 1996.  p.507 ; and subsection

21f Sauer J. In Comprehensive Heterocyclic Chemistry II, Tetrazines   Vol. 6:  Katritzky AR. Rees CW. Scriven EF. Pergamon Press; NY: 1996.  p.901 

22 Perrin DD. Armarego WLF. Purification of Laboratory Chemicals   Pergamon; NY: 1992. 

23a Krass DK. Chen TK. Paudler WW. J. Heterocycl. Chem.  1973,  10:  343 

23b Krass DK. Chen TK. Paudler WW. J. Heterocycl. Chem.  1974,  11:  43 

23c Neunhoeffer H. Frühauf HW. Liebigs Ann. Chem.  1972,  102-103:  760