Rapid access to the "in,out"-tetracyclic core of ingenol

Angewandte Chemie - International Edition

Volumn 44, Issue 1, 2004, Pages 121-123

  Epstein, Oleg L ^a   Jin, Kun Cha ^a  

^a WAYNE STATE UNIVERSITY   (United States)

Author keywords

Epoxidation; Natural products; Rearrangement; Ring closing metathesis; Terpenoids

Indexed keywords

3 CHLOROPERBENZOIC ACID; ALKENE; INGENOL; LEWIS ACID;

ARTICLE; CHEMICAL BOND; CHEMICAL STRUCTURE; CHROMATOGRAPHY; EPIMER; EPOXIDATION; ISOMER; PINACOL REARRANGEMENT; RING CLOSING METATHESIS; STEREOCHEMISTRY;

ALKENES; CYCLIZATION; DITERPENES; INDICATORS AND REAGENTS; MOLECULAR STRUCTURE; STEREOISOMERISM;

EID: 11244300691     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200461807     Document Type: Article

References (51)

1. a) K. Zechmeister, F. Brandl, W. Hoppe, E. Hecker, H. J. Opferkuch, W. Adolf, Tetrahedron Lett. 1970, 11, 4075;
2. b) H. J. Opferkuch, E. Hecker, Tetrahedron Lett. 1974, 15, 261;
3. c) E. Hecker, Pure Appl. Chem. 1977, 49, 1423.
4. a) Y. Nishizuka, Science 1986, 233, 305;
5. b) A. M. Jeffery, R. M. J. Liskamp, Proc. Natl. Acad. Sci. USA 1986, 83, 241;
6. c) P. A. Wender, K. F. Koehler, N. A. Sharkey, M. L. Dell'Aquila, P. M. Blumberg, Proc. Natl. Acad. Sci. USA 1986, 83, 4214;
7. d) H. Nakamura, Y. Kishi, M. A. Pajares, R. R. Rando, Proc. Natl. Acad. Sci. USA 1989, 86, 9672.
8. a) S. M. Kupchan, I. Uchida, A. R. Branfman, R. G. Dailey, Jr., B. Y. Fei, Science 1976, 191, 571;
9. b) M. Fujiwara, K. Ijichi, K. Tokuhisa, K. Katsuura, S. Shigeta, K. Konno, G. Y. S. Wang, D. Uemura, T. Yokota, M. Baba, Antimicrob. Agents Chemother. 1996, 40, 271;
10. c) M. Fujiwara, K. Ijichi, K. Tokuhisa, K. Katsuura, G.-Y.-S. Wang, D. Uemura, S. Shigeta, K. Konno, T. Yokota, M. Baba, Antiviral Chem. Chemother. 1996, 7, 230.
11. For a total synthesis of 2, see: a) P. A. Wender, H. Kogen, H. Y. Lee, J. D. Munger, Jr., R. S. Wilhelm, P. D. Williams, J. Am. Chem. Soc. 1989, 111, 8957; b) P. A. Wender, F. E. McDonald, J. Am. Chem. Soc. 1990, 112, 4956; c) P. A. Wender, K. D. Rice, M. E. Schnute, J. Am. Chem. Soc. 1997, 119, 7897.
12. For a total synthesis of 2, see: a) P. A. Wender, H. Kogen, H. Y. Lee, J. D. Munger, Jr., R. S. Wilhelm, P. D. Williams, J. Am. Chem. Soc. 1989, 111, 8957; b) P. A. Wender, F. E. McDonald, J. Am. Chem. Soc. 1990, 112, 4956; c) P. A. Wender, K. D. Rice, M. E. Schnute, J. Am. Chem. Soc. 1997, 119, 7897.
13. For a total synthesis of 2, see: a) P. A. Wender, H. Kogen, H. Y. Lee, J. D. Munger, Jr., R. S. Wilhelm, P. D. Williams, J. Am. Chem. Soc. 1989, 111, 8957; b) P. A. Wender, F. E. McDonald, J. Am. Chem. Soc. 1990, 112, 4956; c) P. A. Wender, K. D. Rice, M. E. Schnute, J. Am. Chem. Soc. 1997, 119, 7897.
14. For a formal synthesis of 2, see: K. Lee, J. K. Cha, J. Am. Chem. Soc. 2001, 123, 5590.
15. For excellent reviews, see: a) S. Kim, J. D. Winkler, Chem. Soc. Rev. 1997, 26, 387; b) R. W. Alder, S. P. East, Chem. Rev. 1996, 96, 2097.
16. For excellent reviews, see: a) S. Kim, J. D. Winkler, Chem. Soc. Rev. 1997, 26, 387; b) R. W. Alder, S. P. East, Chem. Rev. 1996, 96, 2097.
17. a) R. L. Funk, T. A. Olmstead, M. Parvez, J. Am. Chem. Soc. 1988, 110, 3298;
18. b) R. L. Funk, T. A. Olmstead, M. Parvez, J. B. Stallman, J. Org. Chem. 1993, 55, 5873;
19. c) J. H. Rigby, V. de Sainte Claire, S. V. Cuisiat, M. J. Heeg, J. Org. Chem. 1996, 61, 7992;
20. d) J. H. Rigby, B. Bazin, J. H. Meyer, F. Mohammadi, Org. Lett. 2002, 4, 799;
21. e) H. Kigoshi, Y. Suzuki, K. Aoki, D. Uemura, Tetrahedron Lett. 2000, 41, 3927;
22. f) H. Tang, N. Yusuff, J. L. Wood, Org. Lett. 2001, 3, 1563.
23. For stereocontrolled construction of an ingenol prototype that has cis stereochemistry, see: L. A. Paquette, R. J. Ross, J. P. Springer, J. Am. Chem. Soc. 1988, 110, 6192.
24. J. D. Winkler, M. B. Rouse, M. F. Greaney, S. J. Harrison, Y. T. Jeon, J. Am. Chem. Soc. 2002, 124, 9726.
25. K. Tanino, K. Onuki, K. Asano, M. Miyashita, T. Nakamura, Y. Takahashi, I. Kuwajima, J. Am. Chem. Soc. 2003, 125, 1498.
26. a) K. Maruoka, M. Hasegawa, H. Yamamoto, K. Suzuki, M. Shimazaki, G.-i. Tsuchihashi, J. Am. Chem. Soc. 1986, 108, 3827;
27. b) T. Saito, T. Suzuki, M. Morimoto, C. Akiyama, T. Ochiai, K. Takeuchi, T. Matsumoto, K. Suzuki, J. Am. Chem. Soc. 1998, 120, 11633;
28. c) T. Nagasawa, K. Taya, M. Kitamura, K. Suzuki, J. Am. Chem, Soc. 1996, 118, 8949, and references therein.
29. For a general review, see: a) D. J. Coveney, "The Semipinacol and Other Rearrangements" in Comprehensive Organic Synthesis, Vol. 3 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, UK, 1991, Chap. 3.4, pp. 777-801; For recent studies from other laboratories, see; b) C. M. Marson, A. J. Walker, J. Pickering, A. D. Hobson, R. Wrigglesworth, S. J. Edge, J. Org. Chem. 1993, 58, 5944; c) M. E. Jung, D. C. D'Amico, J. Am. Chem. Soc. 1995, 117, 7379; d) C.-A. Fan, B.-M. Wang, Y.-Q. Tu, Z.-L. Song, Angew. Chem. 2001, 113, 4020; Angew. Chem. Int. Ed. 2001, 40, 3877.
30. For a general review, see: a) D. J. Coveney, "The Semipinacol and Other Rearrangements" in Comprehensive Organic Synthesis, Vol. 3 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, UK, 1991, Chap. 3.4, pp. 777-801; For recent studies from other laboratories, see; b) C. M. Marson, A. J. Walker, J. Pickering, A. D. Hobson, R. Wrigglesworth, S. J. Edge, J. Org. Chem. 1993, 58, 5944; c) M. E. Jung, D. C. D'Amico, J. Am. Chem. Soc. 1995, 117, 7379; d) C.-A. Fan, B.-M. Wang, Y.-Q. Tu, Z.-L. Song, Angew. Chem. 2001, 113, 4020; Angew. Chem. Int. Ed. 2001, 40, 3877.
31. For a general review, see: a) D. J. Coveney, "The Semipinacol and Other Rearrangements" in Comprehensive Organic Synthesis, Vol. 3 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, UK, 1991, Chap. 3.4, pp. 777-801; For recent studies from other laboratories, see; b) C. M. Marson, A. J. Walker, J. Pickering, A. D. Hobson, R. Wrigglesworth, S. J. Edge, J. Org. Chem. 1993, 58, 5944; c) M. E. Jung, D. C. D'Amico, J. Am. Chem. Soc. 1995, 117, 7379; d) C.-A. Fan, B.-M. Wang, Y.-Q. Tu, Z.-L. Song, Angew. Chem. 2001, 113, 4020; Angew. Chem. Int. Ed. 2001, 40, 3877.
32. For a general review, see: a) D. J. Coveney, "The Semipinacol and Other Rearrangements" in Comprehensive Organic Synthesis, Vol. 3 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, UK, 1991, Chap. 3.4, pp. 777-801; For recent studies from other laboratories, see; b) C. M. Marson, A. J. Walker, J. Pickering, A. D. Hobson, R. Wrigglesworth, S. J. Edge, J. Org. Chem. 1993, 58, 5944; c) M. E. Jung, D. C. D'Amico, J. Am. Chem. Soc. 1995, 117, 7379; d) C.-A. Fan, B.-M. Wang, Y.-Q. Tu, Z.-L. Song, Angew. Chem. 2001, 113, 4020; Angew. Chem. Int. Ed. 2001, 40, 3877.
33. For a general review, see: a) D. J. Coveney, "The Semipinacol and Other Rearrangements" in Comprehensive Organic Synthesis, Vol. 3 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, UK, 1991, Chap. 3.4, pp. 777-801; For recent studies from other laboratories, see; b) C. M. Marson, A. J. Walker, J. Pickering, A. D. Hobson, R. Wrigglesworth, S. J. Edge, J. Org. Chem. 1993, 58, 5944; c) M. E. Jung, D. C. D'Amico, J. Am. Chem. Soc. 1995, 117, 7379; d) C.-A. Fan, B.-M. Wang, Y.-Q. Tu, Z.-L. Song, Angew. Chem. 2001, 113, 4020; Angew. Chem. Int. Ed. 2001, 40, 3877.
34. For reviews on enantioselective construction of quaternary centers, see: a) K. Fuji, Chem. Rev. 1993, 93, 2037; b) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402; Angew. Chem. Int. Ed. 1998, 37, 388; c) J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725; Angew. Chem. Int. Ed. 2001, 40, 4591.
35. For reviews on enantioselective construction of quaternary centers, see: a) K. Fuji, Chem. Rev. 1993, 93, 2037; b) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402; Angew. Chem. Int. Ed. 1998, 37, 388; c) J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725; Angew. Chem. Int. Ed. 2001, 40, 4591.
36. For reviews on enantioselective construction of quaternary centers, see: a) K. Fuji, Chem. Rev. 1993, 93, 2037; b) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402; Angew. Chem. Int. Ed. 1998, 37, 388; c) J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725; Angew. Chem. Int. Ed. 2001, 40, 4591.
37. For reviews on enantioselective construction of quaternary centers, see: a) K. Fuji, Chem. Rev. 1993, 93, 2037; b) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402; Angew. Chem. Int. Ed. 1998, 37, 388; c) J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725; Angew. Chem. Int. Ed. 2001, 40, 4591.
38. For reviews on enantioselective construction of quaternary centers, see: a) K. Fuji, Chem. Rev. 1993, 93, 2037; b) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402; Angew. Chem. Int. Ed. 1998, 37, 388; c) J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725; Angew. Chem. Int. Ed. 2001, 40, 4591.
39. a) A recent total synthesis of 1 by Kuwajima and co-workers also utilized a Tsuchihashi-Suzuki rearrangement, but in a different ring system (see ref [10];
40. b) A retropinacol rearrangement of ingenol to a tigliane derivative was known (see also ref [1c]): G. Appendino, G. C. Tron, G. Cravotto, G. Palmisano, R. Annunziata, G. Baj, N. Surico, Eur. J. Org. Chem. 1999, 3413;
41. c) See also: L. A. Paquette, Z. Zhao, F. Gallou, J. Liu, J. Am. Chem. Soc. 2000, 122, 1540.
42. It may be noted that our successful synthesis of (+)-asteltoxin evolved from a biosynthetic postulate that featured a related 1,2-alkyl shift: a) K. D. Eom, J. V. Raman, H. Kim, J. K. Cha, J. Am. Chem. Soc. 2003, 125, 5415; b) J. V. Raman, H. K. Lee, R. Vleggaar, J. K. Cha, Tetrahedron Lett. 1995, 36, 3095.
43. It may be noted that our successful synthesis of (+)-asteltoxin evolved from a biosynthetic postulate that featured a related 1,2-alkyl shift: a) K. D. Eom, J. V. Raman, H. Kim, J. K. Cha, J. Am. Chem. Soc. 2003, 125, 5415; b) J. V. Raman, H. K. Lee, R. Vleggaar, J. K. Cha, Tetrahedron Lett. 1995, 36, 3095.
44. For reviews, see: a) R. H. Grubbs, S. J. Miller, G. C. Fu, Acc. Chem. Res. 1995, 28, 446; b) A. Fürstner, K. Langemann, Synthesis 1997, 792; c) D. S. La, J. B. Alexander, D. R. Cefalo, D. D. Graf, A. H. Hoveyda, R. R. Schrock, J. Am. Chem. Soc. 1998, 120, 9720, and references therein.
45. For reviews, see: a) R. H. Grubbs, S. J. Miller, G. C. Fu, Acc. Chem. Res. 1995, 28, 446; b) A. Fürstner, K. Langemann, Synthesis 1997, 792; c) D. S. La, J. B. Alexander, D. R. Cefalo, D. D. Graf, A. H. Hoveyda, R. R. Schrock, J. Am. Chem. Soc. 1998, 120, 9720, and references therein.
46. For reviews, see: a) R. H. Grubbs, S. J. Miller, G. C. Fu, Acc. Chem. Res. 1995, 28, 446; b) A. Fürstner, K. Langemann, Synthesis 1997, 792; c) D. S. La, J. B. Alexander, D. R. Cefalo, D. D. Graf, A. H. Hoveyda, R. R. Schrock, J. Am. Chem. Soc. 1998, 120, 9720, and references therein.
47. a) L. A. Paquette, R. J. Ross, Y. J. Shi, J. Org. Chem. 1990, 55, 1589;
48. b) A. Sekine, N. Kumagai, K. Uotsu, T. Ohshima, M. Shibasaki, Tetrahedron Lett. 2000, 41, 509.
49. For a review, see: A. R. Chamberlin, S. H. Bloom, Org. React. 1990, 39, 1.
50. a) The crystal structure of 8 can be found in the Supporting Information;
51. b) We thank Dr. Fook Tham at the University of California, Riverside for X-ray crystallographic analysis.