Studies on the biomimetic synthesis of the manzamine alkaloids

Chemistry - A European Journal

Volumn 5, Issue 11, 1999, Pages 3154-3161

  Baldwin, Jack E ^a   Claridge, Timothy D W ^a   Culshaw, Andrew J ^a   Heupel, Florian A ^a   Lee, Victor ^a   Spring, David R ^a   Whitehead, Roger C ^a  

^a UNIVERSITY OF OXFORD   (United Kingdom)

Author keywords

Biomimetic synthesis; Diels Alder reaction; Keramaphidin B; Manzamine; Natural products

Indexed keywords

ALKALOID DERIVATIVE; MANZAMINE A;

ARTICLE; BIOSYNTHESIS; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE;

EID: 0032725566     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/(sici)1521-3765(19991105)5:11<3154::aid-chem3154>3.0.co;2-7     Document Type: Article

References (76)

1. Subsequent reports have described another twenty five related alkaloids, including manzamines D, E, F, G, H, J, K (K = G), L, M, X and Y, and hydroxy, dihydro, tetrahydro and other derivatives. Reviews: a) R. J. Andersen, R. W. M. Van Soest, F. Kong, Alkaloids: Chemical and Biological Perspectives, Vol. 10 (Ed.: S.W. Pelletier), Pergamon, London, 1996, pp. 301-355;
2. b) M. Tsuda, J. Kobayashi, Heterocydes 1997, 46, 765-794;
3. c) N. Matzanke, R. J. Gregg, S. M. Weinreb, Org. Prep. Proceed. Int. 1998, 30, 1-52;
4. some recent additions include: d) J. Kobayashi, D. Watanabe, N. Kawasaki, M. Tsuda, J. Org. Chem. 1997, 62, 9236-9239;
5. e) Y. Guo, E. Trivellone, G. Scognamiglio, G. Cimmo, Tetrahedron 1998, 54, 541-550;
6. f) F. Kong, E. I. Graziani, R. J. Andersen, J. Nat. Prod. 1998, 61, 267-271;
7. g) M. Tsuda, D. Watanabe, J. Kobayashi, Tetrahedron Lett. 1998, 39, 1207-1210;
8. h) D. Watanabe, M. Tsuda, J. Kobayashi, J. Nat. Prod. 1998, 61, 689-692;
9. i) R. J. Clark, K. L. Field, R. D. Charan, M. J. Garson, I. M. Brereton, A. C. Willis, Tetrahedron 1998, 54, 8811-8826;
10. j) M. Tsuda, D. Watanbe, J. Kobayashi, Heterocycles 1999, 50, 485-488; for a review on the synthesis of the manzamines see: E. Magnier, Y. Langlois, Tetrahedron 1998, 54, 6201-6258.
11. j) M. Tsuda, D. Watanbe, J. Kobayashi, Heterocycles 1999, 50, 485-488; for a review on the synthesis of the manzamines see: E. Magnier, Y. Langlois, Tetrahedron 1998, 54, 6201-6258.
12. Two total synthesis of manzamine A (1) have recently been disclosed: k) J. D. Winkler, J. M. Axten, J. Am. Chem. Soc. 1998, 120, 6425-6426;
13. l) S. F. Martin, J. M. Humphery, A. Ali, M. C. Hillier, J. Am. Chem. Soc. 1999, 121, 866-867.
14. R. Sakai, T. Riga, C. W. Jefford, G. Bernardinelli, J. Am. Chem. Soc. 1986, 108, 6404-6405.
15. R. E. Longley, O. J. McConnell, E. Essich, D. Harmody, J. Nat. Prod. 1993, 56, 915-920.
16. R. Sakai, S. Kohmoto, T. Higa, C. W. Jefford, G. Bernardinelli, Tetrahedron Lett. 1987, 28, 5493-5496.
17. M. J. Garson, Nat. Prod. Rep. 1989, 6, 143-170.
18. J. E. Baldwin, R. C. Whitehead, Tetrahedron Lett. 1992, 33, 2059-2062.
19. K. Kondo, H. Shigemori, Y. Kikuchi, M. Ishibashi, T. Sasaki, J. Kobayashi, J. Org. Chem. 1992, 57, 2480-2483.
20. a) J. Kobayashi, M. Tsuda, N. Kawasaki, K. Matsumoto, T. Adachi, Tetrahedron Lett. 1994, 35, 4383-4386;
21. b) M. Tsuda, K. Inaba, N. Kawasaki, K. Honma, J. Kobayashi, Tetrahedron 1996, 52, 2319-2324;
22. c) J. Kobayashi, N. Kawasaki, M. Tsuda, Tetrahedron Lett. 1996, 37, 8203-8204;
23. d) F. Kong, R. J. Andersen, Tetrahedron 1995, 51, 2895-2906. (+)-Keramaphidin B has the opposite absolute stereochemistry as that shown for 10 in Figure 2.
24. For a preliminary report see: J. E. Baldwin, T. D. W. Claridge, A. J. Culshaw, F. A Heupel, V. Lee, D. R. Spring, R. C. Whitehead, R. J. Boughtflower, I. M. Mutton, R. J. Upton, Angew. Chem. 1998, 110, 2806-2808; Angew. Chem. Int. Ed. 1998, 37, 2661-2663.
25. For a preliminary report see: J. E. Baldwin, T. D. W. Claridge, A. J. Culshaw, F. A Heupel, V. Lee, D. R. Spring, R. C. Whitehead, R. J. Boughtflower, I. M. Mutton, R. J. Upton, Angew. Chem. 1998, 110, 2806-2808; Angew. Chem. Int. Ed. 1998, 37, 2661-2663.
26. If the cycloaddition occurs in the absence of enzyme catalysis, a racemic mixture will result. Alternatively: i) an enzyme may catalyse the cycloaddition, but with limited enantiomeric differentiation since both enantiomers are present; or ii) two enzymes catalyse the cycloaddition with antipodal selectivity. To achieve the unequal enantiomeric mixture a kinetic resolution may occur, the (-)-antipode being processed to the ircinals and manzamines faster than the (+)-antipode is processed to its products.
27. Model studies: a) J. E. Baldwin, T. D. W. Claridge, F. A. Heupel, R. C. Whitehead, Tetrahedron Lett. 1994, 55, 7829-7832;
28. b) J. E. Baldwin, T. D. W. Claridge, A. J. Culshaw, F. A. Heupel, S. Smrckova, R. C. Whitehead, Tetrahedron Lett. 1996, 37, 6919-6922;
29. c) J. E. Baldwin, L. Bischoff, T. D. W. Claridge, F. A. Heupel, D. R. Spring, R. C. Whitehead, Tetrahedron 1997, 53, 2271-2290;
30. d) L. Gil, A. Gateau-Olesker, C. Marazano, B. C. Das, Tetrahedron Lett. 1995, 36, 707-710;
31. e) L. Gil, A. Gateau-Olesker, Y.-S. Wong, L. Chernatova, C. Marazano, B. C. Das, Tetrahedron Lett. 1995, 36, 2059-2062;
32. f) L. Gil, X. Baucherel, M.-T. Martin, C. Marazano, B. C. Das, Tetrahedron Lett. 1995, 36, 6231-6234.
33. a) J. B. Cloke, F. J. Pilgrim, J. Am. Chem. Soc. 1939, 61, 2667-2669;
34. b) I. J. Borowitz, G. J. Williams, L. Gross, R. Rapp, J Org. Chem. 1968, 33, 2013-2020;
35. c) J. F. Oughton, Chem. Abstr. 1964, 60, P4011h;
36. d) P. S. Manchand, R. A. Micheli, S. J. Saposnik, Tetrahedron 1992,48, 9391-9398;
37. e) A. I. Meyers, E. W. Collington, Tetrahedron 1971, 27, 5979-5985.
38. a) A. J. Mancuso, D. Swern, Synthesis 1981, 165-185;
39. b) T. T. Tidwell, Synthesis 1990, 857-870.
40. a) A. D. Buss, S. Warren, J. Chem. Soc. Perkin Trans. I 1985, 2307-2325;
41. b) P. M. Ayrey, M. A. Bolton, A. D. Buss, N. Greeves, D. Levin, P. Wallace, S. Warren, J. Chem. Soc. Perkin Trans. I 1992, 3407-3417.
42. a) B. E. Maryanoff, A. B. Reitz, B. A. Duhl-Emswiler, J. Am. Chem. Soc. 1985, 107, 217-226;
43. N2 step.
44. N. Miyashita, A. Yoshikoshi, P. A. Grieco, J. Org. Chem. 1977, 42, 3772-3774.
45. A. V. R. Rao, G. R. Reddy, B. V. Rao, J. Org. Chem. 1991, 56, 4545-4547.
46. G. W. Kabalka, M. Varma, R. S. Varma, J. Org. Chem. 1986, 51, 2386-2388.
47. a) A. Ahond, A. Cave, C. Kan-Fan, H.-P. Husson, J. de-Rostolan, P. Potier, J. Am. Chem. Soc. 1968, 90, 5622-5623;
48. b) M. Lounasmaa, A. Koskinen, Heterocycles 1984, 22, 1591-1612.
49. 1H NMR and LCMS to detect the presence and approximate quantity of keramaphidin B (10); SDS: sodium dodecyl sulfate; CHAPS: 3-[(cholamidopropyl)dimethylammonio]-1-propanesulfonate.
50. 13C NMR, LCMS and by doping the synthetic sample with authentic material (see Supporting Information);
51. R. J. Sundberg, D. S. Grierson, H.-P. Husson, J. Org. Chem. 1984, 49, 2400-2404.
52. The conformational search was carried out with 10000 Monte Carlo steps in MacroModel V5.5. Each conformer was minimised with the MM2* force field in water; F. Mohamadi, N. G. J. Richards, W. C. Guida, R. Liskamp, M. Lipton, C. Caufield, G. Chang, T. Hendrickson, W. C. Still, J. Comput. Chem. 1990, 11, 440-467.
53. Structure 25 was calculated from an ab initio transition state search at the RHF/6-31G* level. Note that the transition state structure is highly asynchronous, where the formation of one bond is far advanced and the other is in the initial stages.
54. The most compelling evidence for a Diels-Alderase comes from work published by Oikawa and co-workers; however, the enzyme still has to be fully purified and characterised; see: a) A. Ichihara, H. Oikawa, Biosci. Biotech. Biochem. 1997, 67, 12-18;
55. b) K. Katayama, T. Kobayashi, H. Oikawa, Honma, A. Ichihara, Biochim. Biophys. Acta 1998, 1354, 387-395;
56. c) H. Oikawa, T. Kobayashi, K. Katayma, Y. Suzuki, A. Ichihara, J. Org. Chem. 1998, 63, 8748-8756;
57. d) H. Oikawa, Y. Suzuki, K. Katayama, A. Naga, C. Sakano, A. Ichihara, J. Chem. Soc. Perkin Trans. I 1999, 1225-1232.
58. F. H. Westheimer, Adv. Enzymol. 1962, 24, 441-482.
59. All other routes, such as those involving pyridin-2-ones as dienes, were unsuccessful in model systems.
60. A. Kaiser, X. Billot, A. Gateau-Olesker, C. Marazano, B. C. Das, J. Am. Chem. Soc. 1998, 120, 8026-8034.
61. 5-Amino-2,4-pentadienals are formally ring-opened pyridines, although Marazano and co-workers proposed that they would be biosynthesised from the condensation of malondialdehyde, an aldehyde and an amino group. For convenience, the dienophile illustrated in Scheme 4 is a tetrahydropyridine. However, Marazano suggested that the dienophile is likely to be a 2,3-dihydropyridinium ion or another 5-amino-2,4-pentadienal.
62. J. Becher, Synthesis 1980, 589.
63. 1,3-Dimethylpyridinium salts have been treated with alkaline ferri-cyanide in the Decker oxidation to provide the pyridone in 70-82% yield (H. Decker, Chem. Ber. 1892, 25, 443; H. Weber, Adv. Heterocycl. Chem. 1987, 41, 275-317). It is presumed that the mechanism involves the formation of the "pseudo base", that is a hydroxide-pyridinium adduct. Moreover, the pseudo base is deprotonated before the rate determining complex formation with ferricyanide. If the mechanism is correct, then the formation of the deprotonated pseudo base can occur reversibly with 28, but ring-opening is not favoured due to the lack of an electron-withdrawing group on the nitrogen.
64. 1,3-Dimethylpyridinium salts have been treated with alkaline ferri-cyanide in the Decker oxidation to provide the pyridone in 70-82% yield (H. Decker, Chem. Ber. 1892, 25, 443; H. Weber, Adv. Heterocycl. Chem. 1987, 41, 275-317). It is presumed that the mechanism involves the formation of the "pseudo base", that is a hydroxide-pyridinium adduct. Moreover, the pseudo base is deprotonated before the rate determining complex formation with ferricyanide. If the mechanism is correct, then the formation of the deprotonated pseudo base can occur reversibly with 28, but ring-opening is not favoured due to the lack of an electron-withdrawing group on the nitrogen.
65. J. Becher, L. Finsen, I. Winckelmann, Tetrahedron 1981, 37, 2375-2378. To form the correct 5-amino-2,4-pentadienal 27 hydroxide is required to attack the pyridine C6 position.
66. Other glutaconaldehyde derivatives have been investigated and used as dienes in the Diels-Alder reaction; see: a) E. J. J. Grabowski, R. L. Autrey, Tetrahedron 1969, 25, 4315-4330;
67. b) J. Becher, H. C. Nielsen, J. P. Jacobsen, O. Simonsen, H. Clausen, J. Org. Chem. 1988, 53, 1862-1871;
68. c) L. Berthon, A. Tahri, D. Uguen, Tetrahedron Lett. 1994, 35, 3937-3940.
69. For reviews on ring-closing metathesis see: a) R. H. Grubbs, S. J. Miller, G. C. Fu, Acc. Chem. Res. 1995, 28, 446-452;
70. b) H.-G. Schmalz, Angew. Chem. 1995, 107, 1981-1984; Angew. Chem. Int. Ed. Engl. 1995, 34, 1833-1836;
71. b) H.-G. Schmalz, Angew. Chem. 1995, 107, 1981-1984; Angew. Chem. Int. Ed. Engl. 1995, 34, 1833-1836;
72. c) A. Fürstner, K. Langemann, Synthesis 1997, 792-803;
73. d) S. K. Armstrong, J. Chem. Soc. Perkin Trans. I 1998, 371-388.
74. Since the Grubbs catalyst 32 is not compatible completely with tertiary amines, the cycloadduct was protected as its bis-hydrochloride salt (G. C. Fu, S. T. Nguyen, R. H. Grubbs, J. Am. Chem. Soc. 1993, 115, 9856-9857). However, when the salt was treated with 32 then the quantity of keramaphidin B (10) was reduced (LCMS).
75. Attempts to close the 13-membered ring in tetracyclic 31 with the Schrock catalyst mainly resulted in decomposition. Similar results were observed when the Grubbs catalyst was used with 31 and its bishydrochloride salt.
76. 2, 7]dodec-11-ene ring systems.