Asteltoxin S.L. Schreiber 1983 - Michigan State …...Conclusion/Summary •Since discovery the...

AsteltoxinS.L. Schreiber 1983

1

Schreiber, S.L.; Hoveyda, A.H.; Wu, H.-J. J. Am. Chem. Soc. 1983, 105, 660.

The Beginning

2Ciamician, G.; Silber, P. Ber. Dtsch. Chem. Ges. 1908, 41, 1928.

Paterno, E.; Chieffi, G. Gazz. Chim. Ital. 1909, 39, 341

The Beginning contd.

3

Cookson, R.C.; Crundwell, E.; Hudec, J. Chem. Ind. (London) 1958, 1003. Eaton, P.E.; Cole, T.W., Jr. J Am. Chem. Soc 1964, 86, 962

Eaton, P.E.; Cole, T.W., Jr. ibid. 1964, 86, 3157.

Paterno-Buchi reaction

4

Paterno, E.; Chieffi, G. Gazz. Chim. Ital. 1909, 39, 341 Buchi, G.; Inman, C.G.; Lipinsky, E.S. J. Am. Chem. Soc. 1954, 76, 4327

Buchi, G.; Goldman, I.M. ibid. 1957, 79, 4741Schroeter, S.H.; Orlando, C.M., J. Org. Chem. 1969, 34, 1181

Schroeter, S.H. ibid. 1969, 34, 1188Maurizio, D.; Rocco R. Molecules 2013, 18, 11384-1142.

5

Schreiber, S.L.; Hoveyda, A.H.; Wu, H.-J. J. Am. Chem. Soc. 1983, 105, 660.

6Schreiber, S.L.; Hoveyda, A.H.; Wu, H.-J. J. Am. Chem. Soc. 1983, 105, 660.

Retrobreakdown

7

Total Synthesis

8

9

10

11Grieco, P.A.; Gilman, S.; Nishizawa, M. J. Org. Chem. 1976, 41, 1485

12Corey, E.J.; Hoover, D.J. Tetrahedron Lett. 1982, 23, 3463.

13

Cram, D.J.; Abd Elhafez, F.A. J. Am Chem. Soc. 1952, 74, 5828Cram, D.J.; Kopecky, K.R. ibid. 1959, 81, 2748.

Marti-Castro, A.N, Chem. Rev. 2004, 104, 2939−3002

14

15

Pummerer rearrangement 26-27

De Lucchi, O.; Miotti, U.’ Modena, G. Org React. (N.Y.) 1991, 40, 157Moiseenkov, A.M.; Dragan, V.A.; Veselovskii, V.V. Russ. Chem. Rev. (Engl. Transl.) 1991, 60, 643.

Smith, Laura H. S.; Coote, Susannah C.; Sneddon, Helen F.; Procte, David J.; Angew. Chem. Int. Ed. 2010, 49, 5832–5844

16

Conclusion/Summary

• Since discovery the Paterno-Buchi process it hasbecome a tool used in highly oxygenated and stereochemically complex molecules

• It has been cited 94 times according to Web of Science.

• The feasibility and speed of the photo induced reaction makes it a perfect viable process for natural product synthesis.

17

Recent total synthesis from Wayne State!

• Eom, K. D., Raman, J. V., Kim, H., & Cha, J. K. (2003). Total synthesis of (+)-asteltoxin. Journal of the American Chemical Society, 125(18), 5415-5421

18

Acknowledgements

Dr. Maleczka

Walker Lab

Kio

19

Questions?

20