A short and efficient total synthesis of the naturally occurring coumarins siderin, kotanin, isokotanin A and desertorin C

Synthesis

Volumn , Issue 12, 2003, Pages 1803-1808

  Hüttel, Wolfgang ^a   Nieger, Martin ^b   Müller, Michael ^a  

^a FORSCHUNGSZENTRUM JÜLICH   (Germany)

^b UNIVERSITY OF BONN   (Germany)

Author keywords

Atropisomerism; Biaryls; Natural coumarins; Oxidative phenolic coupling

Indexed keywords

ISOMERS; SYNTHESIS (CHEMICAL);

OXIDATIVE COUPLING;

DIMERS;

COUMARIN DERIVATIVE; DESERTORIN C; ISOKOTANIN A; KOTANIN; NATURAL PRODUCT; SIDERIN; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; DRUG STRUCTURE; DRUG SYNTHESIS; ISOMERISM; STRUCTURE ANALYSIS; TECHNIQUE;

EID: 0141854143     PISSN: 00397881     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2003-41027     Document Type: Article

References (37)

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4. 2,4b,7a
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8. Siderin(1): (a) Venturella, P.; Bellino, A.; Piozzi, F. Tetrahedron Lett. 1974, 15, 979. (b) Chexal, K. K.; Fouweather, C.; Holker, J. S. E. J. Chem. Soc., Perkin Trans. 1 1974, 554. (c) Ahluwalia, V. K.; Kumar, D. Indian J. Chem., Sect. B 1976, 14, 589.
9. Siderin(1): (a) Venturella, P.; Bellino, A.; Piozzi, F. Tetrahedron Lett. 1974, 15, 979. (b) Chexal, K. K.; Fouweather, C.; Holker, J. S. E. J. Chem. Soc., Perkin Trans. 1 1974, 554. (c) Ahluwalia, V. K.; Kumar, D. Indian J. Chem., Sect. B 1976, 14, 589.
10. Siderin(1): (a) Venturella, P.; Bellino, A.; Piozzi, F. Tetrahedron Lett. 1974, 15, 979. (b) Chexal, K. K.; Fouweather, C.; Holker, J. S. E. J. Chem. Soc., Perkin Trans. 1 1974, 554. (c) Ahluwalia, V. K.; Kumar, D. Indian J. Chem., Sect. B 1976, 14, 589.
11. Kotanin(2) (a) Racemic: Büchi, G.; Klaubert, D. H.; Shank, R. C.; Weinreb, S. M.; Wogan, G. N. J. Org. Chem. 1971, 36, 1143. (b) Stereoselective: Lin, G.-Q.; Zhong, M. Tetrahedron: Asymmetry 1997, 8, 1369.
12. Kotanin(2) (a) Racemic: Büchi, G.; Klaubert, D. H.; Shank, R. C.; Weinreb, S. M.; Wogan, G. N. J. Org. Chem. 1971, 36, 1143. (b) Stereoselective: Lin, G.-Q.; Zhong, M. Tetrahedron: Asymmetry 1997, 8, 1369.
13. Isokotanin A(3) (a) Racemic: Lin, G.-Q.; Zhong, M. Acta Chim. Sin. 1997, 55, 97; Chem. Abstr. 1997, 126, 211942. (b) Stereoselective: Lin, G.-Q.; Zhong, M. Tetrahedron Lett. 1996, 37, 3015. (c) Stereoselective: Bringmann, G.; Hinrichs, J.; Henschel, P.; Kraus, J.; Peters, K.; Peters, E.-M. Eur. J. Org. Chem. 2002, 1096.
14. Isokotanin A(3) (a) Racemic: Lin, G.-Q.; Zhong, M. Acta Chim. Sin. 1997, 55, 97; Chem. Abstr. 1997, 126, 211942. (b) Stereoselective: Lin, G.-Q.; Zhong, M. Tetrahedron Lett. 1996, 37, 3015. (c) Stereoselective: Bringmann, G.; Hinrichs, J.; Henschel, P.; Kraus, J.; Peters, K.; Peters, E.-M. Eur. J. Org. Chem. 2002, 1096.
15. Isokotanin A(3) (a) Racemic: Lin, G.-Q.; Zhong, M. Acta Chim. Sin. 1997, 55, 97; Chem. Abstr. 1997, 126, 211942. (b) Stereoselective: Lin, G.-Q.; Zhong, M. Tetrahedron Lett. 1996, 37, 3015. (c) Stereoselective: Bringmann, G.; Hinrichs, J.; Henschel, P.; Kraus, J.; Peters, K.; Peters, E.-M. Eur. J. Org. Chem. 2002, 1096.
16. Isokotanin A(3) (a) Racemic: Lin, G.-Q.; Zhong, M. Acta Chim. Sin. 1997, 55, 97; Chem. Abstr. 1997, 126, 211942. (b) Stereoselective: Lin, G.-Q.; Zhong, M. Tetrahedron Lett. 1996, 37, 3015. (c) Stereoselective: Bringmann, G.; Hinrichs, J.; Henschel, P.; Kraus, J.; Peters, K.; Peters, E.-M. Eur. J. Org. Chem. 2002, 1096.
17. Desertorin C(4) (a) Racemic: Rizzacasa, M. A.; Sargent, M. V. J. Chem. Soc., Perkin Trans. 1 1988, 2425. (b) Stereoselective: Kyasnoor, R. V.; Sargent, M. V. Chem. Commun. 1998, 2713. (c) Steroselective: Baker, R. W.; Kyasnoor, R. V.; Sargent, M. V.; Skelton, B. W.; White, A. H. Aust. J. Chem. 2000, 53, 487.
18. Desertorin C(4) (a) Racemic: Rizzacasa, M. A.; Sargent, M. V. J. Chem. Soc., Perkin Trans. 1 1988, 2425. (b) Stereoselective: Kyasnoor, R. V.; Sargent, M. V. Chem. Commun. 1998, 2713. (c) Steroselective: Baker, R. W.; Kyasnoor, R. V.; Sargent, M. V.; Skelton, B. W.; White, A. H. Aust. J. Chem. 2000, 53, 487.
19. Desertorin C(4) (a) Racemic: Rizzacasa, M. A.; Sargent, M. V. J. Chem. Soc., Perkin Trans. 1 1988, 2425. (b) Stereoselective: Kyasnoor, R. V.; Sargent, M. V. Chem. Commun. 1998, 2713. (c) Steroselective: Baker, R. W.; Kyasnoor, R. V.; Sargent, M. V.; Skelton, B. W.; White, A. H. Aust. J. Chem. 2000, 53, 487.
20. The total syntheses of the three biaryl coumarins 2-4 require ca. 25 steps according to the literature.
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24. Similar reactions are reported in the literature. However, yields are low and reaction conditions cannot be applied to substrate 6., e.g.: Connor, D. T.; Sorenson, R. J. J. Heterocycl. Chem. 1981, 18, 587.
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30. 7b,8.
31. 7b,8.
32. This was demonstrated for the 6,8′-bisaminochromenone 15, which was converted to desertorin C (4) in a single step. Hence, the hydrolytic mixture was dehydrated chemically with dimethyl carbonate after no starting material could be detected (TLC). Acetyl chloride was added to generate additional HCl. The yield (34%) is comparable to the overall yield of the two-step procedure (36%).
33. The low yield in the case of M-(-)-2 is mainly due to a nonoptimized reaction time for acidic hydrolysis.
34. 11a
35. (a) Chiarello, J.; Joullié, M. M. Tetrahedron 1988, 44, 41.
36. (b) Sala, T.; Sargent, M. V. J. Chem. Soc., Perkin Trans. Trans. 1 1981, 855.
37. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-215646. Copies of the data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: int. code+44-1223/336-033; e-mail: deposit@ccdc.cam.ac.uk].