Regioselective cyclizations of delocalized 1,3-amide dianions with oxalic acid dielectrophiles

Liebigs Annales

Volumn , Issue 12, 1997, Pages 2553-2561

  Langer, Peter ^a,c   Döring, Manfred ^b   Görls, Helmar ^b   Beckert, Rainer ^b  

^a UNIVERSITY OF GÖTTINGEN   (Germany)

^b FRIEDRICH SCHILLER UNIVERSITY JENA   (Germany)

^c UNIVERSITY OF CAMBRIDGE   (United Kingdom)

Author keywords

Ambident dianions; Nitrogen heterocycles; Radialenes; Spiro compounds; Tautomerism

Indexed keywords

EID: 33749023622     PISSN: 09473440     EISSN: None     Source Type: Journal    
DOI: 10.1002/jlac.199719971220     Document Type: Article

References (55)

1. Review: [1a] A. Maercker, Methoden Org. Chem. (Hauben-Weyl), 4th ed., vol. E19d, 1993, 448-566. -
2. [1b] C. M. Thompson, D. Green, Tetrahedron 1991, 47, 4223-4285.
3. For the preparation of alicycles using symmetric dianions: [2a] K. G. Bilyard, P. J. Garratt, R. Hunter, E. Lete, J. Org. Chem. 1982, 47, 4731-4736. -
4. See also: [2b] R. B. Bates, B. Gordon, T. K. Highsmith, J. J. White, J. Org. Chem. 1984, 49, 2981-2987. -
5. For organometallics: [2c] A. Maercker, A. Groos, Angew. Chem. 1996, 108, 216-218;
6. Angew. Chem. Int. Ed. Engl. 1996, 35, 210-212. -
7. For macrocyles: [2d] B. König, M. Rödel, P. Bubenitschek, P. G. Jones, Angew. Chem 1995, 107, 752-754;
8. Angew. Chem. Int. Ed. Engl. 1995, 34, 661-662.
9. Interest has been recently directed at unsymmetric dianions: [3a] D. Seyferth, T. Wang, W. M. Davis, Organometallics 1994, 13, 4134-4136. -
10. [3b] K. Tanaka, H. Horiuchi, H. Yoda, J. Org. Chem. 1989, 54, 63-70. -
11. For an early example: [3c] V. Ehrig, D. Seebach, Chem. Ber. 1975, 108, 1961-1973.
12. [4a] C. C. Chiu, F. Jordan J. Org. Chem. 1994, 59, 5763-5766.
13. - [4b] J. Fabian, H. Nakazumi, M. Matsuoka, Chem. Rev. 1992, 92, 1197-1226. -
14. [4c] H. tom Dieck, J. Dietrich, Chem. Ber. 1984, 117, 694-701.
15. [5a] I. T. Barnish, C. R. Hauser, J. Org. Chem. 1968, 33, 2116-2118. -
16. For a review on Y-aromaticity: [5b] J. Klein, Tetrahedron 1983, 39, 2733-2759.
17. We refer to ambident dianions as to systems bearing two delocalized negative charges, in the generation of which at least one abstraction of a proton attached to a carbon is involved.
18. -3 mol/1) was added a THF solution (30 ml) of bis-lithiated acetanilide at -78°C within 0.5 h (for the diester) or within 5 h (for both dichloride and diester) using a perfusor. The temperature was allowed to rise to 20°C within 4 h. Workup followed the procedure for the preparation of 1 giving a viscos, yellow to brown, ether-insoluble material which could not be purified by chromatography. The same result was obtained using those concentrations for diester and dianion as given for the preparation of 1 (see Experimental Section).
19. [8a] D. Lindauer, R. Beckert, M. Döring, P. Fehling, H. Görls, J. Prakt. Chem., 1995, 337, 143-152, and literature cited herein.
20. - [8b] M. Wenzel, D. Lindauer, R. Beckert, R. Boese, E. Anders, Chem. Ber. 1996, 129, 39-44. -
21. [8c] For reduction of 1,4-diazadienes see: J. Scholz, B. Richter, R. Goddard, C. Krüger, Chem. Ber. 1993, 126, 57-61 and literature cited herein. For complexation: see ref.[4c].
22. [9a] Tetramic acids are pharmaceutically active groups and occur in a variety of nature products: B. J. L. Royles, Chem. Rev. 1995, 95, 1981-2001. -
23. [9b] Compound Ic has been previously prepared by a different approach: A. Roedig, W. Ritschel, D. Scheutzow, H. J. Hecht, Chem. Ber. 1982, 115, 2652-2663.
24. [10a] This is concluded from the regioselectivity observed for the reaction of amide-dianions with monofunctional alkylhalides: see ref.[5a]. -
25. -3 mol/l) solution of BTIOC, when the dianion solution was added within 1.5 h and, surprisingly, when the reaction was carried out at -78°C (warming within 2 h).
26. 2C(N=H)Ph in 43% yield, see ref.[5a]
27. Open-chained tricarbonyl methane derivatives are rather unstable and only a few derivatives have been described so far: [12a] R. W. Saalfrank, A. Stark, M. Bremer, H.-U. Hummel, Angew. Chem. 1990, 102, 292-295;
28. Angew. Chem. Int. Ed. Engl., 1990, 29, 311-314. -
29. [12b] H.-D. Stachel, M. Schorp, L. Maier, K. Dandl, Liebigs Ann. Chem. 1994, 1121-1127.
30. [13a] For reviews on radialenes: H. Hopf, G. Maas, Angew. Chem., 1992, 104, 953-977;
31. Angew. Chem. Int. Ed. Engl. 1992, 31, 931. -
32. [13b] G. Maas, H. Hopf, in The Chemistry of Dienes and Polyenes, vol. I (Ed.: Z. Rappoport), Wiley, 1997, p. 927-977.
33. elec denotes the energy resulting from the electrostatic term. -
34. rel can be explained by less severe steric interactions of aryl substituents in case of the spiro structure core. -
35. -1] of structures A, B, C, D, E, F, and of the seven-membered ring isomer are 0.00, -13.58, -0.04, -5.42, 8.78, 14.35, and -1.19, respectively.
36. Nitrogen-rich spiro heterocycles are of interest in view of photochromic properties: C. Dorweiler, M. Holderbaum, T. Munzmay, P. Spang, H. Dürr, C. Krüεr, E. Raabe, Chem. Ber. 1988, 121, 843-851.
37. [16a] M. J. Nolte, P. S. Steyn, P. L. Wessels, J. Chem. Soc., Perkin Trans 1 1980, 1057-1065. -
38. [16b] J. V. Barkley, J. M. Markopoulos, O. Markopoulou, J. Chem. Soc., Perkin Trans 2 1994, 1271-1274 and literature cited herein.
39. c = 10°C. -
40. -1 (see ref.[18]).
41. 3 group connected to a hydrogen bonded carbonyl or to a free carbonyl have been reported for an open-chained β-aminoamide: M. Basato, R. Campostrini, B. Corain, B. Loneato, S. Sitran, A. C. Veronese, G. Vale, J. Chem. Soc., Perkin Trans 2 1985, 2019-2025.
42. 2 group, i.e. tautomer D.
43. For all tricarbonylmethanes 2, deshielding of quaternary carbon C-α is drastically decreased due to the four neighboring heteroatoms. Carbon C-γ is deshielded (with respect to 1), presumably due to π-acceptor properties of the tricarbpnylmethane moiety. Conjugation effects also should be responsible for shifting the carbonyl signal to higher field (with respect to 1 and 3a). The quaternary carbons of the arylimino group attached to C-β and C-γ (C-β″ and C-γ″, respectively) appear at lower field for 2c than for 1e (Ar = Ph). The same is true for 2a with respect to 1b (Ar = Tol). The difference between chemical shifts of 1 and 2 is much smaller for carbon C-β than for C-γ but in a similar range for carbons C-β″ and C-γ″. This suggests that an imino rather than an amino group is attached to C-β or that the nitrogen participates in strong hydrogen bonding.
44. The parameters of the heteroatoms have been quoted according to: A. Streitwieser, Molecular Orbital Theory, Wiley: New York, 1967.
45. See also: D. L. Boger, S. M. Weinreb, Hetero Diets-Alder Methodology in Organic Synthesis, Academic Press: San Diego, 1987;
46. R. Hoffmann, J. Chem. Phys., 1963, 39, 1397. For the hetero Diels-Alder reaction of 2a the relative stability was calculated to 2.8280 β in favor of the activated complex deriving from tautomer A (using ethylene as dienophile).
47. 15N-NMR spectroscopy: G. Scherer, H.-H. Limbach, J. Am. Chem. Soc. 1994, 116, 1230-1239. All attempts to obtain single crystals of 2 suitable for X-ray crystal structure analysis unfortunately proved unsuccessful so far.
48. [23a] L. Lopez, M. Berlekamp, D. Kowalski, G. Erker, Angew. Chem. 1994, 106, 1168-1170,
49. Angew. Chem. Int. Ed. Engl. 1994, 33, 1114-1116. -
50. [23b] G. Erker, M. Riedel, S. Koch, T. Jödicke, E.-U. Würthwein, J. Org. Chem. 1995, 60, 5284-5290 and literature cited herein.
51. K. Schwetlick, Organikum, Deutscher Verlag der Wissenschaften: Berlin, 1990.
52. MOLEN, An Interactive Structure Solution Procedure, Enraf-Nonius, Delft, The Netherlands, 1990.
53. G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467-473.
54. G. M. Sheldrick, University of Göttingen, Germany, 1993.
55. Further details of the crystal structure investigations are available on requests from the Fachinformationszentrum Karlsruhe, Gesellschaft für wissenschaftlich-technische Information mbH, D-76344 Eggenstein-Leopoldshafen, on quoting the depository number CSD-407271, the names of the authors, and the journal citation.