Short biomimetic synthesis of a steroid by photoinduced electron transfer and remote asymmetric induction [2]

Journal of the American Chemical Society

Volumn 121, Issue 20, 1999, Pages 4894-4895

  Heinemann, Christoph ^a   Demuth, Martin ^a  

^a MAX PLANCK INSTITUTE FOR CHEMICAL ENERGY CONVERSION   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

DIOXINONE DERIVATIVE; STEROID; UNCLASSIFIED DRUG;

BINDING SITE; BIOSYNTHESIS; CHIRALITY; CYCLIZATION; ELECTRON TRANSPORT; LETTER; LIGHT; PROTON NUCLEAR MAGNETIC RESONANCE; STEROIDOGENESIS; STRUCTURE ANALYSIS;

EID: 0033606254     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja984035z     Document Type: Letter

References (39)

1. For general references to PET, see: (a) Photoinduced Electron Transfer; Fox, M. A., Chandon, M., Eds.; Elsevier: New York, 1988; Parts A-C.
2. (b) Kavarnos, G. Fundamentals of Photoinduced Electron Transfer, Wiley-VCH: New York, 1993.
3. (c) Hintz, S.; Heidbreder, A.; Mattay, J. Top. Curr. Chem. 1996, 177, 77-124.
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8. Xing, X. Ph.D. Thesis, Max-Planck-Institut für Strahlenchemie/ University of Essen, 1998.
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11. Preparation of 4 and 7: The (E,E,E)-geranylgeranylmethyl dioxinones 4 and 7 were prepared from (E,E,E,)-geranylgeranyl bromide and the chiral spirocyclic dioxinone moieties in one step. Details can be found in the Supporting Information; see also ref 6.
12. Heinemann, C. Ph.D. Thesis, Max-Planck-Institut für Strahlenchemie/ University of Essen, 1998.
13. 2O 10:1, 330 mL) of 7 (1.9 g, 3.7 mmol), biphenyl (0.45 g, 2.9 mmol) and 1,4-dicyanotetramethyl-benzene (0.22 g, 1.2 mmol) (for preparation, see: (a) Suzuki, H.; Nakamura, K.; Goto, R. Bull. Chem. Soc. Jpn. 1966, 39, 128-131.
14. 2/EtOAc) and HPLC separation (Nucleosil-7-100, cyclohexane/2-propanol 100:1) gave 163 mg (0.31 mmol, 8%) of 8 and 74 mg (0.14 mmol, 4%) of 9, each as a white solid and > 95% pure by NMR. The structures of 8 and 9 were secured, besides IR, EI MS, and elemental analysis, by NOE and NOESY spectroscopy (see Supporting Information and ref 6).
15. Heinemann, C.; Warzecha, K.-D.; Xing, X.; Demuth, M. Ind. J. Chem. 1997, 36, 494-497.
16. Heinemann, C.; Demuth, M. J. Am. Chem. Soc. 1997, 119, 1129-1130.
17. For the synthesis, availability, applications and patents of the dioxinone moieties as well as the facial selectivity in [2 + 2]-cycloadditions, see: (a) Demuth, M.; Palomer, A.; Sluma, H.-D.; Dey, A. K.; Krüger, C.; Tsay, Y.-H. Angew. Chem. 1986, 98, 1093-1095; Angew. Chem., Int. Ed. Engl. 1986, 25, 1117-1119.
18. For the synthesis, availability, applications and patents of the dioxinone moieties as well as the facial selectivity in [2 + 2]-cycloadditions, see: (a) Demuth, M.; Palomer, A.; Sluma, H.-D.; Dey, A. K.; Krüger, C.; Tsay, Y.-H. Angew. Chem. 1986, 98, 1093-1095; Angew. Chem., Int. Ed. Engl. 1986, 25, 1117-1119.
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20. (c) Demuth, M. In Photochemical Key Steps in Organic Synthesis; Mattay, J., Griesbeck, A. G., Eds.; VCH: Weinheim, 1994; pp 92-96.
21. (d) Preparation and use are patented: Demuth, M.; Schaffner, K. EPPS 0254239; U.S. Patents 5,026,877, 5,142,054, and 4,864,037.
22. Parts of these results have been communicated at the 17th IUPAC Symposium on Photochemistry, Sitges, Spain, 1998.
23. 13C NMR analysis, and is about the same for the isolated pure products.
24. Further products identified in a related study stem from disproportionation, dimerization, and hydroxylation of the polyalkene, cf. ref 3.
25. For precoiling in cationic cyclization processes, see: (a) Johnson, W. S. Angew. Chem. 1976, 88, 33-66; Angew. Chem., Int. Ed. Engl. 1976, 15, 9.
26. For precoiling in cationic cyclization processes, see: (a) Johnson, W. S. Angew. Chem. 1976, 88, 33-66; Angew. Chem., Int. Ed. Engl. 1976, 15, 9.
27. (b) Macco, A. A.; Buck, H. M. J. Org. Chem. 1981, 46, 2655-2660.
28. (c) Bartlett, P. A. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1984; Vol. 3, Part B, pp 341-409.
29. 3 and measurement of optical rotations. Details can be found in the Supporting Information.
30. 3.
31. For some recent examples of remote asymmetric inductions, see: (a) Tanaka, K.; Ohta, Y.; Fuji, K. J. Org. Chem. 1995, 60, 8036-8043,
32. (b) Stanway, S. J.; Thomas, E. J. Synlett 1995, 214-216.
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36. (f) Molander, G. A.; McWilliams, J. C.; Noll, B. C. J. Am. Chem. Soc. 1997, 119, 1265-1276.
37. (g) ref 8.
38. The shortest, albeit not asymmetric, synthesis of a steroid has in the past been performed in a one-pot multicomponent procedure: Posner, G. H.; Mallamo, J. P.; Black, A. Y. Tetrahedron 1981, 37, 3921-3926.
39. The title expression steroid refers in the present case to steroidal skeletons embodying additional three methyls at C(4) and C(8) which derive from the readily available starting terpenoid polyalkene used for convenience.