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DOI: 10.1055/s-0040-1707372
An Improved Synthesis of 3,6-Dihydro-as-indacene
The authors are grateful for the financial support from Fondo Nacional de Desarrollo Científico y Tecnológico, Chile (FONDECYT) (Grants 1161297, EQM120021, EQM130032, EQM150102), the Pontificia Universidad Católica de Chile (PUC) (Grant 3913-541-81), the Scheduled Tribes Welfare Department, Government of Karnataka, India for a student fellowship (Y.D.) to pursue a research stay at the Pontificia Universidad Católica de Chile. E.M. (ICMAB) acknowledges the Severo Ochoa Program, Ministerio de Economía y Competitividad (MINECO) (SEV-2015-0496).
Abstract
This contribution describes an updated synthetic route to 3,6-dihydro-as-indacene along with full characterization of all intermediates. The title compound is prepared by Mannich condensation of 2-methylfuran with formaldehyde and dimethylamine hydrochloride, quaternization of the resulting amine with methyl iodide, and conversion into the ammonium hydroxide salt by treatment with silver oxide in water. Subsequent Hoffmann elimination and [6,6]-cycloaddition through pyrolysis produces a furanocyclophane, which after photooxidation, intramolecular cycloaddition, and dehydration with sodium carbonate affords 2,3,6,7-tetrahydro-1,8-dione-as-indacene. Reduction of this diketone gives a mixture of alcohols, which after dehydration under slightly basic or acidic conditions produces 3,6-dihydro-as-indacene. The structure is confirmed by X-ray diffraction, and all intermediates are characterized by means of 1H and 13C NMR spectroscopy.
Key words
as-indacene - [6,6]-cycloaddition - polycyclic bridged ligand - bimetallic ligand - Mannich condensation - Hoffmann eliminationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1707372.
- Supporting Information
Publication History
Received: 11 June 2020
Accepted after revision: 11 August 2020
Article published online:
02 September 2020
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References
- 1a Katz TJ, Balogh V, Schulman J. J. Am. Chem. Soc. 1968; 90: 734
- 1b Hafner K. Angew. Chem., Int. Ed. Engl. 1964; 3: 165
- 1c Erden I, Xu FP, Sadoun A, Smith W, Sheff G, Ossun M. J. Org. Chem. 1995; 60: 813
- 1d Wightman RH, Wain RJ, Lake DH. Can. J. Chem. 1977; 49: 1360
- 2 Ceccon A, Bisello A, Crociani L, Gambaro A, Ganis P, Manoli F, Santi S, Venzo A. Organomet. Chem. 2000; 600: 94
- 3 Ceccon A, Santi S, Orian L, Bisello A. Coord. Chem. Rev. 2004; 248: 683
- 4 Manríquez JM, Ward MD, Reiff WM, Calabrese JC, Jones NL, Carroll PJ, Bunel EE, Miller JS. J. Am. Chem. Soc. 1995; 117: 6182
- 5 Santi S, Orian L, Durante C, Bencze EZ, Bisello A, Donoli A, Ceccon A, Benetollo F, Crociani L. Chem. Eur. J. 2007; 13: 7933
- 6 Santi S, Ceccon A, Carli F, Crociani L, Bisello A, Tiso M, Venzo A. Organometallics 2002; 21: 2679
- 7 Aguirre-Etcheverry P, O’Hare D. Chem. Rev. 2010; 110: 4839
- 8 Iijma S, Motoyama I, Sano H. Chem. Lett. 1979; 1349
- 9 Trogen L, Ulf E. Acta Chem. Scand. 1979; B33: 109
- 10 Bell WL, Curtis CJ, Eigenbrot CW, Pierpont CG, Robbins JL, Smart JC. Organometallics 1987; 6: 266
- 11 Dahrouch MR, Jara PL, Portilla Y, Abril D, Alfonso G, Chavez I, Manriquez JM, Riviere BM, Castel A. Organometallics 2011; 20: 5591
- 12 Barlow S, O’Hare D. Organometallics 1996; 15: 3483
- 13 Ceccon A, Crociani L, Santi S, Venzo A, Biffisc A, Boccaletti G. Tetrahedron Lett. 2002; 43: 8475
- 14 Faúndez R, Castillo F, Preite M, Schott E, Zarate X, Manriquez JM, Molins E, Morales-Verdejo C, Chávez I. Synthesis 2019; 51: 441
- 15 Holdren RF, Hixon RM. J. Am. Chem. Soc. 1946; 68: 1198
- 16 Wasserman H. H., Doumaux A. R. Jr. 1962; 84: 4611
- 17 Vandyck K, Matthys B, Van der Eycken J. Tetrahedron Lett. 2005; 46: 75
- 18 Kuppens T, Vandyck K, Van der Eycken J, Herrebout W. J. Org. Chem. 2005; 70: 9103
- 19 Armarego WL. F, Chai CL. L. In Purification of Laboratory Chemicals, 6th ed. Elsevier; Oxford: 2009
- 20 Blessing RH. Acta Cryst. 1995; A51: 33
- 21 Sheldrick GM. Acta Cryst. 2015; C71: 3
- 22 Farrugia LJ. J. Appl. Cryst. 2012; 45: 849