A New Approach to the Total Synthesıs of (±)-Nordasycarpıdone by Rıng-closure wıth Tetrachloro-1,4-benzoquınone

Authors

DOI:

https://doi.org/10.20450/mjcce.2020.1736

Keywords:

dasycarpidone, uleine, nordasycarpidone, 1, 5-methanoazacino[4, 3-b]indole

Abstract

A new synthetic route for the  (±)-nordasycarpidone was achieved in five steps with an overall yield of  41%. This route involves  ring closure and formation of 5 which has a  methanoazocino[4,3-b]indole skeleton in the key step. The reaction also involved a cyclization reaction of  tetrahydrocarbazole with a monoalkyl nitrile side chain at the C-2 position, and this reaction was mediated by tetrachloro-1,4-benzoquinone (TCB). The central step in the synthesis was  the closure of the D-ring of the intra-molecular structure and the addition of amine, which resulted in an aza-tetracyclic substructure that contained the ABCD-ring of the strychnos alkaloid family.

Author Biography

Nesimi Uludag, Tekirdag Namık kemal University

Departmen of Chemistry

References

F. Tang, M. G. Banwell, A. C. Willis, Palladium-catalyzed Ullmann Cross-Coupling/Tandem reductive cyclization route to key members of the uleine alkaloid family, J. Org. Chem. 81, 2950–2957 (2016).

DOI: https://doi.org/10.1021/acs.joc.6b00240

R. Akdag, Y. Ergun, Y. A new synthetic route to the synthesis of nordasycarpidone derivatives, J. Heterocycl. Chem. 44, 863–866 (2007).

DOI: https://doi.org/10.1002/jhet.5570440418

M. Amat, S. Hadida, G. Pshenichnyi., J. Bosch, Palladium(0)-catalyzed heteroarylation of 2- and 3-indolylzinc derivatives. An efficient general method for the preparation of (2-pyridyl)indoles and their application to indole alkaloid synthesis, J. Org. Chem. 62, 3158–3175 (1997).

DOI: https://doi.org/10.1021/jo962169u

J. Gracia, N. Casamitjana, J. Bonjoch, Total synthesis of uleine-type and strychnos alkaloids through a common intermediate, J. Org. Chem. 59, 3939–3951 (1994). DOI: https://doi.org/10.1021/jo00093a028

J. Bonjoch, N. Casamitjana, J. Gracia, A stereoselective total synthesis of dasycarpidan alkaloids: (±)-dasycarpidone, (±)-dasycarpidol and (±)-nordasycarpidone, J. Chem. Soc. Chem. Commun. 23, 1687–1688 (1991).

DOI: https://doi.org/10.1039/C39910001687

T. P. C. Chierrito, A. C. C. Aguiar, I. M. de Andrade, I. P. Ceravlolo, R. A. C. Gonçalves, A. J. B. de Oliveria, A. U. Krettli, Anti-malarial activity of indole alkaloids isolated from Aspidosperma olivaceum, Malar. J. 13, 142–151 (2014).

DOI: https://doi.org/10.1186/1475-2875-13-142

E. C. Miranda, S. Blechert, S. Gilbertin, Ein neuer Indolalkaloidtyp, Tetrahedron Lett. 23, 5395–5398 (1982).

DOI: https://doi.org/10.1016/0040-4039(82)80139-1

A. Jackson, N. D. V. Wilson, A. J. Gaskel, J. J. A. Joule, The syntheses of (±)-dasycarpidone, (±)-3-epi-dasy¬carpidone, (±)-uleine and (±)-3-epi-uleine, J. Chem. Soc. C, 2738–2747 (1969).

DOI: https://doi.org/10.1039/J39690002738

T. Kametani, T. Suzuki, Syntheses of heterocyclic compounds. CCCXCIV. Total syntheses of (±)-dasycarpidone and (±)-3-epidasycarpidone. Formal total syntheses of (±)-uleine and (±)-3-epiuleine, J. Org. Chem. 36, 1291–1293 (1971).

DOI: https://doi.org/10.1021/jo00808a026

N. Uludag, T. Hökelek, S. Patır, A new approach to the total synthesis of (±)‐20‐epidasycarpidone, J. Heterocycl. Chem. 43, 585–591 (2006).

DOI: https://doi.org/10.1002/jhet.5570430310

N. Uludag, S. Patır, Studies on the synthesis of the azocino[4,3‐b]indole framework and related compounds, J. Heterocycl. Chem. 44, 1317–1322 (2007).

DOI: https://doi.org/10.1002/jhet.5570440613

N. Uludag, R. Yılmaz, O. Asutay, N. Colak, Facile synthesis of the azocino[4,3-b]indole framework of strychnopivotine and other Strychnos alkaloids, Chem. Heterocycl. Compd. 52, 196–199 (2016).

DOI: https://doi.org/10.1007/s10593-016-1860-4

L. J. Dolby, H. Biere, The total synthesis of (±)-da-sycarpidone and (±)-epidasycarpidone, J. Am. Chem. Soc. 90, 2699–2700 (1968).

DOI: https://doi.org/10.1021/ja01012a047

L. Micouin, A. Diez, J. Castells, D. Lopez, M. Rubiralta, J. C. Quirion, H. P. Husson, Synthetic applications of 2-(1,3-dithian-2-yl)indoles V1. Asym-metric synthesis of dasycarpidone-type indole alkaloids, Tetrahedron Lett. 36, 1693–1696 (1995).

DOI: https://doi.org/10.1016/0040-4039(95)00047-G

S. Patır, N. Uludag, A novel Synthetic route for the total synthesis of (±)-uleine, Tetrahedron, 65, 115–118 (2009). DOI: https://doi.org/10.1016/j.tet.2008.10.102

M. Amat, M. Perez, N. Llor, M. Martinelli, E. Molins, J. Bosch, Enantioselective formal synthesis of uleine alkaloids from phenylglycinol-derived bicyclic lactams. Chem. Commun. 35, 1602–1603 (2004).

DOI: https://doi.org/10.1039/B400987H

P. Forns, A. Diez, M. Rubiralta, X. Solans, M. Font-Bardia, Synthetic applications of 2-(1,3-dithian-2-yl)indoles VI.1 Synthesis of 20-epidasycarpidone, Tetrahedron, 52, 3563–3574 (1996).

DOI: https://doi.org/10.1016/0040-4020(96)00033-6

N. Uludag, M. Yakup, Concise Total Synthesis of 20-deethyl-4-demethyldasycarpidone, Org. Prep. Proc. Int. 47, 454–460 (2015).

DOI: https://doi.org/10.1080/00304948.2015.1088756

E. J. Corey, K. Shimoji, Magnesium and zinc-catalyzed thioketalization, Tetrahedron Lett. 24, 169–172 (1983).

DOI: https://doi.org/10.1016/S0040-4039(00)81357-X

J. Bosch, M. Rubiralta, A. Domingo, J. Bolos, A. Linares, C. Minguillon, M. Amat, J. Bonjoch, Synthetic applications of 2-cyano-1,2,3,6-tetrahydropyridines. 2. Synthesis of isodasycarpidone and related systems, the ervitsine skeleton and its benzo analog, J. Org. Chem. 50, 1516–1522 (1985).

DOI: https://doi.org/10.1021/jo00209a031

N. J. Cussans, S. V. Ley, D. H. R. Barton, Removal of thioacetal protecting groups by benzeneseleninic anhydride, J. Chem Soc. Perkin Trans. I, 1654–1657 (1980).

DOI: https://doi.org/10.1039/P19800001654

J. Málek, M. Černý, Reduction of organic compounds by alkoxyaluminohydrides, Synthesis, 5, 217–234 (1972).

DOI: https://doi.org/10.1055/s-1972–21858

C. Höfler, C. Rüchardt, Bimolecular formation of radicals by hydrogen transfer, on the mechanism of quinone dehydrogenations, Liebigs. Ann. 183–188 (1996). DOI: https://doi.org/10.1002/jlac.199619960206

Y. Zhang, C, Li, DDQ-mediated direct cross-dehydrogenative-coupling (CDC) between benzyl ethers and simple ketones, J. Am. Chem. Soc. 128, 4242–4243 (2006). DOI: https://doi.org/10.1021/ja060050p

W. Tu, P. E. Floreangic, Oxidative carbocation formation in macrocycles: Synthesis of the neopeltolide macrocycle, Angew. Chem. Int. Ed. 48, 4567–4571 (2009). DOI: https://doi.org/10.1002/anie.200901489

M. Amat, S. Hadida, N. Llor, S. Sathyanarayana, J. Bosc, Studies on the configurational stability of 3-(2-piperidyl)indoles, J. Org. Chem. 61, 3878–3882 (1996).

DOI: https://doi.org/10.1021/jo952251+

J. A. Joule, M. Ohashi, B. Gilbert, C. Djerassi, Alkaloids studies — LIII: The structures of nine new alkaloids from Aspidosperma dasycarpon A. DC. Tetrahedron, 21, 1717–1734 (1965).

DOI: https://doi.org/10.1016/S0040-4020(01)98642-9

M. C. Mollo, N. Gruber, J. E. Diaz, J. A. Bisceglia, L. R. Orelli, An efficient synthesis of N-alkyl-N-arylputrescines and cadaverines, Org. Prep. Proc. Int. 46, 444–452 (2014).

DOI: https://doi.org/10.1080/00304948.2014.944404

Downloads

Published

2020-05-30

How to Cite

Uludag, N. (2020). A New Approach to the Total Synthesıs of (±)-Nordasycarpıdone by Rıng-closure wıth Tetrachloro-1,4-benzoquınone. Macedonian Journal of Chemistry and Chemical Engineering, 39(1), 11–16. https://doi.org/10.20450/mjcce.2020.1736

Issue

Vol. 39 No. 1 (2020)

Section

Organic Chemistry

License

The authors agree to the following licence: Attribution-NonCommercial 4.0 International (CC BY-NC 4.0)

  • Adapt — remix, transform, and build upon the material
  • for any purpose, even commercially.
The licensor cannot revoke these freedoms as long as you follow the license terms.

 Under the following terms:

  • Attribution — You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use.

  • NonCommercial — You may not use the material for commercial purposes.