Total Synthesis of (±)-Didehydrostemofoline (Asparagamine A) and (±)-Isodidehydrostemofoline

Journal of the American Chemical Society

Volumn 125, Issue 50, 2003, Pages 15284-15285

  Brüggemann, Markus ^a   McDonald, Andrew I ^a,b   Overman, Larry E ^a   Rosen, Mark D ^a,c   Schwink, Lothar ^a,d   Scott, Jeremy P ^a,e  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b Cytokinetics Inc   (United States)

^c JOHNSON AND JOHNSON PHARMACEUTICAL RESEARCH AND DEVELOPMENT   (United States)

^d SANOFI AVENTIS DEUTSCHLAND GMBH   (Germany)

^e Merck Sharp & Dohme Limited   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALKALOID DERIVATIVE; ASPARAGAMINE A; DIDEHYDROSTEMOFOLINE; HERBACEOUS AGENT; ISODIDEHYDROSTEMOFOLINE; NICOTINIC RECEPTOR; STEMOFOLINE; UNCLASSIFIED DRUG; ALKALOID; FUSED HETEROCYCLIC RINGS;

ARTICLE; CHEMICAL REACTION; CHINESE MEDICINE; DIELS ALDER REACTION; DRUG ISOLATION; DRUG STRUCTURE; DRUG SYNTHESIS; MANNICH REACTION; NONHUMAN; PLANT LEAF; PLANT ROOT; POLYMERIZATION; REACTION ANALYSIS; STEREOISOMERISM; TECHNIQUE; CHEMISTRY; STEMONACEAE; SYNTHESIS;

ALKALOIDS; HETEROCYCLIC COMPOUNDS WITH 4 OR MORE RINGS; STEMONACEAE; STEREOISOMERISM;

EID: 0348109461     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0388820     Document Type: Article

References (27)

1. For a recent review, see: Pilli, R. A.; da Conceição Ferreira de Oliveira, M. Nat. Prod. Rep. 2000, 17, 117-127.
2. Irie, H.; Masaki, N.; Ohno, K.; Osaki, K.; Taga, T.; Uyeo, S. J. Chem. Soc., Chem. Commun. 1970, 1066.
3. (a) Sekine, T.; Fukasawa, N.; Kashiwagi, Y.; Ruangrungsi, N.; Murakoshi, I. Chem. Pharm. Bull. 1994, 42, 1360-1362.
4. (b) Sekine, T.; Ikegami, F.; Fukasawa, N.; Kashiwagi, Y.; Aizawa, T.; Fujii, Y.; Ruangrungsi, N.; Murakoshi, I. J. Chem. Soc., Perkin Trans. 1 1995, 391-393.
5. This alkaloid was named asparagamine A by these authors who believed, likely erroneously,7a,c that its plant source was Asparagus racemosus.
6. Jiwajinda, S.; Hirai, N.; Watanabe, K.; Santisopasri, V.; Chuengsamarnyart, N.; Koshimizu, K.; Ohigashi, H. Phytochemistry 2001, 56, 693-695.
7. For recent reports, see: (a) Brem, B.; Seger, C.; Pacher, T.; Hofer, O.; Vajrodaya, S.; Greger, H. J. Agric. Food Chem. 2002, 50, 6383-6388.
8. (b) Godfrey, C.; Benner, J.; Clough, M.; Dunbar, S.; Earley, F.; Russell, A.; Urch, C.; Ware, A. 10th IUPAC International Congress on the Chemistry of Crop Protection 2002, 1, 236.
9. (c) Kaltenegger, E.; Brem, B.; Mereiter, K.; Kalchhauser, H.; Kählig, H.; Hofer, O.; Vajrodaya; S.; Greger, H. Phytochemistry 2003, 63, 803-816.
10. Kende, A. S.; Smalley, T.; Huang, H. J. Am. Chem. Soc. 1999, 121, 7431-7432.
11. For brief reviews, see: (a) Overman, L. E. Acc. Chem. Res. 1992, 25, 352-359.
12. (b) Overman, L. E. Aldrichimica Acta 1995, 28, 107-120.
13. 4 reduction of 3-methoxypyrrole carboxaldehyde: Bellamy, F.; Martz, P.; Streith, J. Heterocycles 1975, 3, 395-400.
14. (a) McMurray, J. E.; Musser, J. Org. Synth. 1977, 56, 65-68.
15. (b) Danishefsky, S.; Prisbylls, M. P.; Hiner, S. J. Am. Chem. Soc. 1978, 100, 2918-2920.
16. (a) For a review of the synthesis of 7-azabicyclo[2.2.1]heptanes, see: Chen, Z.; Trudell, M. L. Chem. Rev. 1996, 96, 1179-1193.
17. (b) Because of their high aromaticity, pyrroles are rarely useful Diels-Alder dienes, cf.: Donnini, C. P.; Just, G. J. Heterocycl. Chem. 1997, 14, 1423-1425.
18. Crystallographic data for this compound have been deposited at the Cambridge Crystallographic Data Centre. (a) Methyl ester analogue: CCDC 220604. (b) Methyl ester analogue: CDCC 220605. (c) Silyl-deprotected hydroiodide salt: CCDC 220606. (d) CCDB 220607. (e) CCDB 220608.
19. Ozonolysis of the ketene silyl acetal derivative of the corresponding ester was complicated by the formation of the α-hydroxy ester.
20. (a) Blakemore, P. R.; Cole, W. J.; Kocienski, P. J.; Morley, A. Synlett 1998, 26-28.
21. (b) Baudin, J. B.; Hareau, G.; Julia, S. A.; Ruel, O. Tetrahedron Lett. 1991, 32, 1175-1178.
22. Prior to workup, DABCO was added to quench unreacted alkylating agent.
23. Such a step eroded the efficiency of the Kende total synthesis of 4.8
24. Knight, D. W.; Pattenden, G. J. Chem. Soc., Perkin Trans. 1 1975, 635-640.
25. Acyl-2(5H)furanones are readily oxidized at C5, see: Pelter, A.; Al-Bayati, R. I. H.; Ayoub, M. T.; Lewis, W.; Pardasani, P.; Hansel, R. J. Chem. Soc., Perkin Trans. 1 1987, 717-742.
26. (a) Corey, E. J.; Winter, R. A. E. J. Am. Chem. Soc. 1963, 85, 2677-2678.
27. 13C NMR and chromatographic properties identical to those of authentic specimens; we are grateful to Professor Suratwadee Jiwajinda (Kasetsart University, Thailand) for a sample of natural 1 and copies of NMR spectra of 3. (b) The structure of 3 was further confirmed by single-crystal X-ray analysis.13e