Enzyme-assisted asymmetric total synthesis of (-)-podophyllotoxin and (- )-picropodophyllin

Journal of Organic Chemistry

Volumn 65, Issue 3, 2000, Pages 847-860

  Berkowitz, David B ^a   Choi, Sungjo ^a   Maeng, Jun Ho ^a  

^a UNIVERSITY OF NEBRASKA LINCOLN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

PODOPHYLLIN; PODOPHYLLOTOXIN;

ARTICLE; CATALYSIS; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHIRALITY; HYDROLYSIS; OXIDATION; REACTION ANALYSIS; SYNTHESIS;

ENZYMES; MAGNETIC RESONANCE SPECTROSCOPY; MOLECULAR STRUCTURE; PODOPHYLLOTOXIN; SPECTROMETRY, MASS, FAST ATOM BOMBARDMENT;

EID: 0033960568     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo991582+     Document Type: Article

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27. For syntheses of (±)-podophyllotoxin, see: (a) Kraus, G. A.; Wu, Y. J. Org. Chem. 1992, 57, 2922-2925. (b) Peterson, J. R.; Hoang, D. D.; Rogers, R. D. Synthesis 1991, 275-277 (c) Jones, D. W.; Thompson, A. M. J. Chem. Soc., Chem. Commun. 1987, 1797-1798. (d) Kaneko, T.; Wong, H. Tetrahedron Lett. 1987, 28, 517-520. (e) Vyas, D. M.; Skonezny, P. M.; Jenks, T. A.; Doyle, T. W. Tetrahedron Lett. 1986, 27, 3099-3102. (f) Macdonald, D. I.; Durst, T. J. Org. Chem. 1988, 51, 4749-4750. (g) Jung, M. E.; Lowen, G. T. Tetrahedron Lett. 1988, 27, 5319-5322. (h) Jung, M. E.; Lam P. Y.; Mansuri, M. M.; Speltz, L. M. J. Org. Chem. 1986, 50, 1087-1105. (i) Van der Eycken, J.; De Clercq, P.; Vandewalle, M. Tetrahedron Lett. 1985, 26, 3871-3874. (j) Rajapaksa, D.; Rodrigo, R. J. Am. Chem. Soc. 1981, 703, 6208-6209. (k) Kende, A. S.; King, M. L.; Curran, D. P. J. Org. Chem. 1981, 46, 2826- 2828. (l) Murphy, W. S.; Wattanasin, S. J. Chem. Soc., Chem. Commun. 1980, 262-263. (m) Kende, A. S.; Liebeskind, L. S.; Mills, J. E.; Rutledge, P. S.; Curran, D. P. J. Am. Chem. Soc. 1977, 99, 7082-7083. (n) Gensler, W. J.; Gastonis, C. G. J. Org. Chem. 1966, 31, 4004-4008.
28. For syntheses of (±)-podophyllotoxin, see: (a) Kraus, G. A.; Wu, Y. J. Org. Chem. 1992, 57, 2922-2925. (b) Peterson, J. R.; Hoang, D. D.; Rogers, R. D. Synthesis 1991, 275-277 (c) Jones, D. W.; Thompson, A. M. J. Chem. Soc., Chem. Commun. 1987, 1797-1798. (d) Kaneko, T.; Wong, H. Tetrahedron Lett. 1987, 28, 517-520. (e) Vyas, D. M.; Skonezny, P. M.; Jenks, T. A.; Doyle, T. W. Tetrahedron Lett. 1986, 27, 3099-3102. (f) Macdonald, D. I.; Durst, T. J. Org. Chem. 1988, 51, 4749-4750. (g) Jung, M. E.; Lowen, G. T. Tetrahedron Lett. 1988, 27, 5319-5322. (h) Jung, M. E.; Lam P. Y.; Mansuri, M. M.; Speltz, L. M. J. Org. Chem. 1986, 50, 1087-1105. (i) Van der Eycken, J.; De Clercq, P.; Vandewalle, M. Tetrahedron Lett. 1985, 26, 3871-3874. (j) Rajapaksa, D.; Rodrigo, R. J. Am. Chem. Soc. 1981, 703, 6208-6209. (k) Kende, A. S.; King, M. L.; Curran, D. P. J. Org. Chem. 1981, 46, 2826- 2828. (l) Murphy, W. S.; Wattanasin, S. J. Chem. Soc., Chem. Commun. 1980, 262-263. (m) Kende, A. S.; Liebeskind, L. S.; Mills, J. E.; Rutledge, P. S.; Curran, D. P. J. Am. Chem. Soc. 1977, 99, 7082-7083. (n) Gensler, W. J.; Gastonis, C. G. J. Org. Chem. 1966, 31, 4004-4008.
29. For syntheses of (±)-podophyllotoxin, see: (a) Kraus, G. A.; Wu, Y. J. Org. Chem. 1992, 57, 2922-2925. (b) Peterson, J. R.; Hoang, D. D.; Rogers, R. D. Synthesis 1991, 275-277 (c) Jones, D. W.; Thompson, A. M. J. Chem. Soc., Chem. Commun. 1987, 1797-1798. (d) Kaneko, T.; Wong, H. Tetrahedron Lett. 1987, 28, 517-520. (e) Vyas, D. M.; Skonezny, P. M.; Jenks, T. A.; Doyle, T. W. Tetrahedron Lett. 1986, 27, 3099-3102. (f) Macdonald, D. I.; Durst, T. J. Org. Chem. 1988, 51, 4749-4750. (g) Jung, M. E.; Lowen, G. T. Tetrahedron Lett. 1988, 27, 5319-5322. (h) Jung, M. E.; Lam P. Y.; Mansuri, M. M.; Speltz, L. M. J. Org. Chem. 1986, 50, 1087-1105. (i) Van der Eycken, J.; De Clercq, P.; Vandewalle, M. Tetrahedron Lett. 1985, 26, 3871-3874. (j) Rajapaksa, D.; Rodrigo, R. J. Am. Chem. Soc. 1981, 703, 6208-6209. (k) Kende, A. S.; King, M. L.; Curran, D. P. J. Org. Chem. 1981, 46, 2826- 2828. (l) Murphy, W. S.; Wattanasin, S. J. Chem. Soc., Chem. Commun. 1980, 262-263. (m) Kende, A. S.; Liebeskind, L. S.; Mills, J. E.; Rutledge, P. S.; Curran, D. P. J. Am. Chem. Soc. 1977, 99, 7082-7083. (n) Gensler, W. J.; Gastonis, C. G. J. Org. Chem. 1966, 31, 4004-4008.
30. For syntheses of (±)-podophyllotoxin, see: (a) Kraus, G. A.; Wu, Y. J. Org. Chem. 1992, 57, 2922-2925. (b) Peterson, J. R.; Hoang, D. D.; Rogers, R. D. Synthesis 1991, 275-277 (c) Jones, D. W.; Thompson, A. M. J. Chem. Soc., Chem. Commun. 1987, 1797-1798. (d) Kaneko, T.; Wong, H. Tetrahedron Lett. 1987, 28, 517-520. (e) Vyas, D. M.; Skonezny, P. M.; Jenks, T. A.; Doyle, T. W. Tetrahedron Lett. 1986, 27, 3099-3102. (f) Macdonald, D. I.; Durst, T. J. Org. Chem. 1988, 51, 4749-4750. (g) Jung, M. E.; Lowen, G. T. Tetrahedron Lett. 1988, 27, 5319-5322. (h) Jung, M. E.; Lam P. Y.; Mansuri, M. M.; Speltz, L. M. J. Org. Chem. 1986, 50, 1087-1105. (i) Van der Eycken, J.; De Clercq, P.; Vandewalle, M. Tetrahedron Lett. 1985, 26, 3871-3874. (j) Rajapaksa, D.; Rodrigo, R. J. Am. Chem. Soc. 1981, 703, 6208-6209. (k) Kende, A. S.; King, M. L.; Curran, D. P. J. Org. Chem. 1981, 46, 2826- 2828. (l) Murphy, W. S.; Wattanasin, S. J. Chem. Soc., Chem. Commun. 1980, 262-263. (m) Kende, A. S.; Liebeskind, L. S.; Mills, J. E.; Rutledge, P. S.; Curran, D. P. J. Am. Chem. Soc. 1977, 99, 7082-7083. (n) Gensler, W. J.; Gastonis, C. G. J. Org. Chem. 1966, 31, 4004-4008.
31. For syntheses of (±)-podophyllotoxin, see: (a) Kraus, G. A.; Wu, Y. J. Org. Chem. 1992, 57, 2922-2925. (b) Peterson, J. R.; Hoang, D. D.; Rogers, R. D. Synthesis 1991, 275-277 (c) Jones, D. W.; Thompson, A. M. J. Chem. Soc., Chem. Commun. 1987, 1797-1798. (d) Kaneko, T.; Wong, H. Tetrahedron Lett. 1987, 28, 517-520. (e) Vyas, D. M.; Skonezny, P. M.; Jenks, T. A.; Doyle, T. W. Tetrahedron Lett. 1986, 27, 3099-3102. (f) Macdonald, D. I.; Durst, T. J. Org. Chem. 1988, 51, 4749-4750. (g) Jung, M. E.; Lowen, G. T. Tetrahedron Lett. 1988, 27, 5319-5322. (h) Jung, M. E.; Lam P. Y.; Mansuri, M. M.; Speltz, L. M. J. Org. Chem. 1986, 50, 1087-1105. (i) Van der Eycken, J.; De Clercq, P.; Vandewalle, M. Tetrahedron Lett. 1985, 26, 3871-3874. (j) Rajapaksa, D.; Rodrigo, R. J. Am. Chem. Soc. 1981, 703, 6208-6209. (k) Kende, A. S.; King, M. L.; Curran, D. P. J. Org. Chem. 1981, 46, 2826- 2828. (l) Murphy, W. S.; Wattanasin, S. J. Chem. Soc., Chem. Commun. 1980, 262-263. (m) Kende, A. S.; Liebeskind, L. S.; Mills, J. E.; Rutledge, P. S.; Curran, D. P. J. Am. Chem. Soc. 1977, 99, 7082-7083. (n) Gensler, W. J.; Gastonis, C. G. J. Org. Chem. 1966, 31, 4004-4008.
32. For syntheses of (±)-podophyllotoxin, see: (a) Kraus, G. A.; Wu, Y. J. Org. Chem. 1992, 57, 2922-2925. (b) Peterson, J. R.; Hoang, D. D.; Rogers, R. D. Synthesis 1991, 275-277 (c) Jones, D. W.; Thompson, A. M. J. Chem. Soc., Chem. Commun. 1987, 1797-1798. (d) Kaneko, T.; Wong, H. Tetrahedron Lett. 1987, 28, 517-520. (e) Vyas, D. M.; Skonezny, P. M.; Jenks, T. A.; Doyle, T. W. Tetrahedron Lett. 1986, 27, 3099-3102. (f) Macdonald, D. I.; Durst, T. J. Org. Chem. 1988, 51, 4749-4750. (g) Jung, M. E.; Lowen, G. T. Tetrahedron Lett. 1988, 27, 5319-5322. (h) Jung, M. E.; Lam P. Y.; Mansuri, M. M.; Speltz, L. M. J. Org. Chem. 1986, 50, 1087-1105. (i) Van der Eycken, J.; De Clercq, P.; Vandewalle, M. Tetrahedron Lett. 1985, 26, 3871-3874. (j) Rajapaksa, D.; Rodrigo, R. J. Am. Chem. Soc. 1981, 703, 6208-6209. (k) Kende, A. S.; King, M. L.; Curran, D. P. J. Org. Chem. 1981, 46, 2826- 2828. (l) Murphy, W. S.; Wattanasin, S. J. Chem. Soc., Chem. Commun. 1980, 262-263. (m) Kende, A. S.; Liebeskind, L. S.; Mills, J. E.; Rutledge, P. S.; Curran, D. P. J. Am. Chem. Soc. 1977, 99, 7082-7083. (n) Gensler, W. J.; Gastonis, C. G. J. Org. Chem. 1966, 31, 4004-4008.
33. For syntheses of (±)-podophyllotoxin, see: (a) Kraus, G. A.; Wu, Y. J. Org. Chem. 1992, 57, 2922-2925. (b) Peterson, J. R.; Hoang, D. D.; Rogers, R. D. Synthesis 1991, 275-277 (c) Jones, D. W.; Thompson, A. M. J. Chem. Soc., Chem. Commun. 1987, 1797-1798. (d) Kaneko, T.; Wong, H. Tetrahedron Lett. 1987, 28, 517-520. (e) Vyas, D. M.; Skonezny, P. M.; Jenks, T. A.; Doyle, T. W. Tetrahedron Lett. 1986, 27, 3099-3102. (f) Macdonald, D. I.; Durst, T. J. Org. Chem. 1988, 51, 4749-4750. (g) Jung, M. E.; Lowen, G. T. Tetrahedron Lett. 1988, 27, 5319-5322. (h) Jung, M. E.; Lam P. Y.; Mansuri, M. M.; Speltz, L. M. J. Org. Chem. 1986, 50, 1087-1105. (i) Van der Eycken, J.; De Clercq, P.; Vandewalle, M. Tetrahedron Lett. 1985, 26, 3871-3874. (j) Rajapaksa, D.; Rodrigo, R. J. Am. Chem. Soc. 1981, 703, 6208-6209. (k) Kende, A. S.; King, M. L.; Curran, D. P. J. Org. Chem. 1981, 46, 2826- 2828. (l) Murphy, W. S.; Wattanasin, S. J. Chem. Soc., Chem. Commun. 1980, 262-263. (m) Kende, A. S.; Liebeskind, L. S.; Mills, J. E.; Rutledge, P. S.; Curran, D. P. J. Am. Chem. Soc. 1977, 99, 7082-7083. (n) Gensler, W. J.; Gastonis, C. G. J. Org. Chem. 1966, 31, 4004-4008.
34. For syntheses of (±)-podophyllotoxin, see: (a) Kraus, G. A.; Wu, Y. J. Org. Chem. 1992, 57, 2922-2925. (b) Peterson, J. R.; Hoang, D. D.; Rogers, R. D. Synthesis 1991, 275-277 (c) Jones, D. W.; Thompson, A. M. J. Chem. Soc., Chem. Commun. 1987, 1797-1798. (d) Kaneko, T.; Wong, H. Tetrahedron Lett. 1987, 28, 517-520. (e) Vyas, D. M.; Skonezny, P. M.; Jenks, T. A.; Doyle, T. W. Tetrahedron Lett. 1986, 27, 3099-3102. (f) Macdonald, D. I.; Durst, T. J. Org. Chem. 1988, 51, 4749-4750. (g) Jung, M. E.; Lowen, G. T. Tetrahedron Lett. 1988, 27, 5319-5322. (h) Jung, M. E.; Lam P. Y.; Mansuri, M. M.; Speltz, L. M. J. Org. Chem. 1986, 50, 1087-1105. (i) Van der Eycken, J.; De Clercq, P.; Vandewalle, M. Tetrahedron Lett. 1985, 26, 3871-3874. (j) Rajapaksa, D.; Rodrigo, R. J. Am. Chem. Soc. 1981, 703, 6208-6209. (k) Kende, A. S.; King, M. L.; Curran, D. P. J. Org. Chem. 1981, 46, 2826- 2828. (l) Murphy, W. S.; Wattanasin, S. J. Chem. Soc., Chem. Commun. 1980, 262-263. (m) Kende, A. S.; Liebeskind, L. S.; Mills, J. E.; Rutledge, P. S.; Curran, D. P. J. Am. Chem. Soc. 1977, 99, 7082-7083. (n) Gensler, W. J.; Gastonis, C. G. J. Org. Chem. 1966, 31, 4004-4008.
35. For syntheses of (±)-podophyllotoxin, see: (a) Kraus, G. A.; Wu, Y. J. Org. Chem. 1992, 57, 2922-2925. (b) Peterson, J. R.; Hoang, D. D.; Rogers, R. D. Synthesis 1991, 275-277 (c) Jones, D. W.; Thompson, A. M. J. Chem. Soc., Chem. Commun. 1987, 1797-1798. (d) Kaneko, T.; Wong, H. Tetrahedron Lett. 1987, 28, 517-520. (e) Vyas, D. M.; Skonezny, P. M.; Jenks, T. A.; Doyle, T. W. Tetrahedron Lett. 1986, 27, 3099-3102. (f) Macdonald, D. I.; Durst, T. J. Org. Chem. 1988, 51, 4749-4750. (g) Jung, M. E.; Lowen, G. T. Tetrahedron Lett. 1988, 27, 5319-5322. (h) Jung, M. E.; Lam P. Y.; Mansuri, M. M.; Speltz, L. M. J. Org. Chem. 1986, 50, 1087-1105. (i) Van der Eycken, J.; De Clercq, P.; Vandewalle, M. Tetrahedron Lett. 1985, 26, 3871-3874. (j) Rajapaksa, D.; Rodrigo, R. J. Am. Chem. Soc. 1981, 703, 6208-6209. (k) Kende, A. S.; King, M. L.; Curran, D. P. J. Org. Chem. 1981, 46, 2826- 2828. (l) Murphy, W. S.; Wattanasin, S. J. Chem. Soc., Chem. Commun. 1980, 262-263. (m) Kende, A. S.; Liebeskind, L. S.; Mills, J. E.; Rutledge, P. S.; Curran, D. P. J. Am. Chem. Soc. 1977, 99, 7082-7083. (n) Gensler, W. J.; Gastonis, C. G. J. Org. Chem. 1966, 31, 4004-4008.
36. For syntheses of (±)-podophyllotoxin, see: (a) Kraus, G. A.; Wu, Y. J. Org. Chem. 1992, 57, 2922-2925. (b) Peterson, J. R.; Hoang, D. D.; Rogers, R. D. Synthesis 1991, 275-277 (c) Jones, D. W.; Thompson, A. M. J. Chem. Soc., Chem. Commun. 1987, 1797-1798. (d) Kaneko, T.; Wong, H. Tetrahedron Lett. 1987, 28, 517-520. (e) Vyas, D. M.; Skonezny, P. M.; Jenks, T. A.; Doyle, T. W. Tetrahedron Lett. 1986, 27, 3099-3102. (f) Macdonald, D. I.; Durst, T. J. Org. Chem. 1988, 51, 4749-4750. (g) Jung, M. E.; Lowen, G. T. Tetrahedron Lett. 1988, 27, 5319-5322. (h) Jung, M. E.; Lam P. Y.; Mansuri, M. M.; Speltz, L. M. J. Org. Chem. 1986, 50, 1087-1105. (i) Van der Eycken, J.; De Clercq, P.; Vandewalle, M. Tetrahedron Lett. 1985, 26, 3871-3874. (j) Rajapaksa, D.; Rodrigo, R. J. Am. Chem. Soc. 1981, 703, 6208-6209. (k) Kende, A. S.; King, M. L.; Curran, D. P. J. Org. Chem. 1981, 46, 2826-2828. (l) Murphy, W. S.; Wattanasin, S. J. Chem. Soc., Chem. Commun. 1980, 262-263. (m) Kende, A. S.; Liebeskind, L. S.; Mills, J. E.; Rutledge, P. S.; Curran, D. P. J. Am. Chem. Soc. 1977, 99, 7082-7083. (n) Gensler, W. J.; Gastonis, C. G. J. Org. Chem. 1966, 31, 4004-4008.
37. For syntheses of (±)-podophyllotoxin, see: (a) Kraus, G. A.; Wu, Y. J. Org. Chem. 1992, 57, 2922-2925. (b) Peterson, J. R.; Hoang, D. D.; Rogers, R. D. Synthesis 1991, 275-277 (c) Jones, D. W.; Thompson, A. M. J. Chem. Soc., Chem. Commun. 1987, 1797-1798. (d) Kaneko, T.; Wong, H. Tetrahedron Lett. 1987, 28, 517-520. (e) Vyas, D. M.; Skonezny, P. M.; Jenks, T. A.; Doyle, T. W. Tetrahedron Lett. 1986, 27, 3099-3102. (f) Macdonald, D. I.; Durst, T. J. Org. Chem. 1988, 51, 4749-4750. (g) Jung, M. E.; Lowen, G. T. Tetrahedron Lett. 1988, 27, 5319-5322. (h) Jung, M. E.; Lam P. Y.; Mansuri, M. M.; Speltz, L. M. J. Org. Chem. 1986, 50, 1087-1105. (i) Van der Eycken, J.; De Clercq, P.; Vandewalle, M. Tetrahedron Lett. 1985, 26, 3871-3874. (j) Rajapaksa, D.; Rodrigo, R. J. Am. Chem. Soc. 1981, 703, 6208-6209. (k) Kende, A. S.; King, M. L.; Curran, D. P. J. Org. Chem. 1981, 46, 2826- 2828. (l) Murphy, W. S.; Wattanasin, S. J. Chem. Soc., Chem. Commun. 1980, 262-263. (m) Kende, A. S.; Liebeskind, L. S.; Mills, J. E.; Rutledge, P. S.; Curran, D. P. J. Am. Chem. Soc. 1977, 99, 7082-7083. (n) Gensler, W. J.; Gastonis, C. G. J. Org. Chem. 1966, 31, 4004-4008.
38. For syntheses of (±)-podophyllotoxin, see: (a) Kraus, G. A.; Wu, Y. J. Org. Chem. 1992, 57, 2922-2925. (b) Peterson, J. R.; Hoang, D. D.; Rogers, R. D. Synthesis 1991, 275-277 (c) Jones, D. W.; Thompson, A. M. J. Chem. Soc., Chem. Commun. 1987, 1797-1798. (d) Kaneko, T.; Wong, H. Tetrahedron Lett. 1987, 28, 517-520. (e) Vyas, D. M.; Skonezny, P. M.; Jenks, T. A.; Doyle, T. W. Tetrahedron Lett. 1986, 27, 3099-3102. (f) Macdonald, D. I.; Durst, T. J. Org. Chem. 1988, 51, 4749-4750. (g) Jung, M. E.; Lowen, G. T. Tetrahedron Lett. 1988, 27, 5319-5322. (h) Jung, M. E.; Lam P. Y.; Mansuri, M. M.; Speltz, L. M. J. Org. Chem. 1986, 50, 1087-1105. (i) Van der Eycken, J.; De Clercq, P.; Vandewalle, M. Tetrahedron Lett. 1985, 26, 3871-3874. (j) Rajapaksa, D.; Rodrigo, R. J. Am. Chem. Soc. 1981, 703, 6208-6209. (k) Kende, A. S.; King, M. L.; Curran, D. P. J. Org. Chem. 1981, 46, 2826- 2828. (l) Murphy, W. S.; Wattanasin, S. J. Chem. Soc., Chem. Commun. 1980, 262-263. (m) Kende, A. S.; Liebeskind, L. S.; Mills, J. E.; Rutledge, P. S.; Curran, D. P. J. Am. Chem. Soc. 1977, 99, 7082-7083. (n) Gensler, W. J.; Gastonis, C. G. J. Org. Chem. 1966, 31, 4004-4008.
39. For syntheses of (±)-podophyllotoxin, see: (a) Kraus, G. A.; Wu, Y. J. Org. Chem. 1992, 57, 2922-2925. (b) Peterson, J. R.; Hoang, D. D.; Rogers, R. D. Synthesis 1991, 275-277 (c) Jones, D. W.; Thompson, A. M. J. Chem. Soc., Chem. Commun. 1987, 1797-1798. (d) Kaneko, T.; Wong, H. Tetrahedron Lett. 1987, 28, 517-520. (e) Vyas, D. M.; Skonezny, P. M.; Jenks, T. A.; Doyle, T. W. Tetrahedron Lett. 1986, 27, 3099-3102. (f) Macdonald, D. I.; Durst, T. J. Org. Chem. 1988, 51, 4749-4750. (g) Jung, M. E.; Lowen, G. T. Tetrahedron Lett. 1988, 27, 5319-5322. (h) Jung, M. E.; Lam P. Y.; Mansuri, M. M.; Speltz, L. M. J. Org. Chem. 1986, 50, 1087-1105. (i) Van der Eycken, J.; De Clercq, P.; Vandewalle, M. Tetrahedron Lett. 1985, 26, 3871-3874. (j) Rajapaksa, D.; Rodrigo, R. J. Am. Chem. Soc. 1981, 703, 6208-6209. (k) Kende, A. S.; King, M. L.; Curran, D. P. J. Org. Chem. 1981, 46, 2826- 2828. (l) Murphy, W. S.; Wattanasin, S. J. Chem. Soc., Chem. Commun. 1980, 262-263. (m) Kende, A. S.; Liebeskind, L. S.; Mills, J. E.; Rutledge, P. S.; Curran, D. P. J. Am. Chem. Soc. 1977, 99, 7082-7083. (n) Gensler, W. J.; Gastonis, C. G. J. Org. Chem. 1966, 31, 4004-4008.
40. (a) Andrews, R. C.; Teague, S. J.; Meyers, A. I. J. Am. Chem. Soc. 1988, 110, 7854-7858.
41. (b) Bush, E. J.; Jones, D. W. J. Chem. Soc., Perkin Trans. 1 1996, 151-155.
42. (c) Charlton, J. L.; Koh, K. J. Org. Chem. 1992, 57, 1514-1516.
43. (d) Van Speybroeck, R.; Guo, H.; Van der Eycken, J.; Vandewalle, M. Tetrahedron 1991, 47, 4675-4682.
44. (e) Hadimani, S. B.; Tanpure, R. P.; Bhat, S. V. Tetrahedron Lett. 1996, 37, 4791-4794.
45. For recent asymmetric syntheses of building blocks toward (-)-podophyllotoxin, see: (a) Brinksma, J.; van der Deen, H.; van Oeveren, A.; Feringa, B. L. J. Chem. Soc., Perkin Trans. 1 1998, 4159-4163. (b) Lautens, M.; Rovis, T. J. Org. Chem. 1997, 62, 5246-5247. (c) Yoshida, S.; Yamanaka, T.; Miyake, T.; Moritani, Y.; Ohmizu, H.; Iwasaki, T. Tetrahedron 1997, 53, 9585-9598.
46. For recent asymmetric syntheses of building blocks toward (-)- podophyllotoxin, see: (a) Brinksma, J.; van der Deen, H.; van Oeveren, A.; Feringa, B. L. J. Chem. Soc., Perkin Trans. 1 1998, 4159-4163. (b) Lautens, M.; Rovis, T. J. Org. Chem. 1997, 62, 5246-5247. (c) Yoshida, S.; Yamanaka, T.; Miyake, T.; Moritani, Y.; Ohmizu, H.; Iwasaki, T. Tetrahedron 1997, 53, 9585-9598.
47. For recent asymmetric syntheses of building blocks toward (-)- podophyllotoxin, see: (a) Brinksma, J.; van der Deen, H.; van Oeveren, A.; Feringa, B. L. J. Chem. Soc., Perkin Trans. 1 1998, 4159-4163. (b) Lautens, M.; Rovis, T. J. Org. Chem. 1997, 62, 5246-5247. (c) Yoshida, S.; Yamanaka, T.; Miyake, T.; Moritani, Y.; Ohmizu, H.; Iwasaki, T. Tetrahedron 1997, 53, 9585-9598.
48. For syntheses of 4-deoxypodophyllotoxin, isopodophyllotoxin, 4-deoxyisopodophyllotoxin, and epiisopodophyllotoxin, see: (a) Hanessian, S.; Ninkovic, S. Can. J. Chem. 1996, 74, 1880-1888. (b) Kuroda, T.; Takahashi, M.; Kondo, K.; Iwasaki, T. J. Org. Chem. 1996, 61, 9560-9563. (c) Bogucki, D. E.; Charlton, J. L. J. Org. Chem. 1995, 60, 588-593. (d) Pelter, A.; Ward, R. S.; Qianrong, L.; Pis, J. Tetrahedron: Asymmetry 1994, 5, 909-920. (e) Itoh, T.; Chika, J.-I.; Takagi, Y.; Nishiyama, S. J. Org. Chem. 1993, 58, 5717-5723. (f) Morimoto, T.; Chiba, M.; Achiwa, K. Tetrahedron 1993, 49, 1793-1806 (g) Choy, W. Tetrahedron 1990, 46, 2281-2286.
49. For syntheses of 4-deoxypodophyllotoxin, isopodophyllotoxin, 4-deoxyisopodophyllotoxin, and epiisopodophyllotoxin, see: (a) Hanessian, S.; Ninkovic, S. Can. J. Chem. 1996, 74, 1880-1888. (b) Kuroda, T.; Takahashi, M.; Kondo, K.; Iwasaki, T. J. Org. Chem. 1996, 61, 9560-9563. (c) Bogucki, D. E.; Charlton, J. L. J. Org. Chem. 1995, 60, 588-593. (d) Pelter, A.; Ward, R. S.; Qianrong, L.; Pis, J. Tetrahedron: Asymmetry 1994, 5, 909-920. (e) Itoh, T.; Chika, J.-I.; Takagi, Y.; Nishiyama, S. J. Org. Chem. 1993, 58, 5717-5723. (f) Morimoto, T.; Chiba, M.; Achiwa, K. Tetrahedron 1993, 49, 1793-1806 (g) Choy, W. Tetrahedron 1990, 46, 2281-2286.
50. For syntheses of 4-deoxypodophyllotoxin, isopodophyllotoxin, 4-deoxyisopodophyllotoxin, and epiisopodophyllotoxin, see: (a) Hanessian, S.; Ninkovic, S. Can. J. Chem. 1996, 74, 1880-1888. (b) Kuroda, T.; Takahashi, M.; Kondo, K.; Iwasaki, T. J. Org. Chem. 1996, 61, 9560-9563. (c) Bogucki, D. E.; Charlton, J. L. J. Org. Chem. 1995, 60, 588-593. (d) Pelter, A.; Ward, R. S.; Qianrong, L.; Pis, J. Tetrahedron: Asymmetry 1994, 5, 909-920. (e) Itoh, T.; Chika, J.-I.; Takagi, Y.; Nishiyama, S. J. Org. Chem. 1993, 58, 5717-5723. (f) Morimoto, T.; Chiba, M.; Achiwa, K. Tetrahedron 1993, 49, 1793-1806 (g) Choy, W. Tetrahedron 1990, 46, 2281-2286.
51. For syntheses of 4-deoxypodophyllotoxin, isopodophyllotoxin, 4-deoxyisopodophyllotoxin, and epiisopodophyllotoxin, see: (a) Hanessian, S.; Ninkovic, S. Can. J. Chem. 1996, 74, 1880-1888. (b) Kuroda, T.; Takahashi, M.; Kondo, K.; Iwasaki, T. J. Org. Chem. 1996, 61, 9560-9563. (c) Bogucki, D. E.; Charlton, J. L. J. Org. Chem. 1995, 60, 588-593. (d) Pelter, A.; Ward, R. S.; Qianrong, L.; Pis, J. Tetrahedron: Asymmetry 1994, 5, 909-920. (e) Itoh, T.; Chika, J.-I.; Takagi, Y.; Nishiyama, S. J. Org. Chem. 1993, 58, 5717-5723. (f) Morimoto, T.; Chiba, M.; Achiwa, K. Tetrahedron 1993, 49, 1793-1806 (g) Choy, W. Tetrahedron 1990, 46, 2281-2286.
52. For syntheses of 4-deoxypodophyllotoxin, isopodophyllotoxin, 4-deoxyisopodophyllotoxin, and epiisopodophyllotoxin, see: (a) Hanessian, S.; Ninkovic, S. Can. J. Chem. 1996, 74, 1880-1888. (b) Kuroda, T.; Takahashi, M.; Kondo, K.; Iwasaki, T. J. Org. Chem. 1996, 61, 9560-9563. (c) Bogucki, D. E.; Charlton, J. L. J. Org. Chem. 1995, 60, 588-593. (d) Pelter, A.; Ward, R. S.; Qianrong, L.; Pis, J. Tetrahedron: Asymmetry 1994, 5, 909-920. (e) Itoh, T.; Chika, J.-I.; Takagi, Y.; Nishiyama, S. J. Org. Chem. 1993, 58, 5717-5723. (f) Morimoto, T.; Chiba, M.; Achiwa, K. Tetrahedron 1993, 49, 1793-1806 (g) Choy, W. Tetrahedron 1990, 46, 2281-2286.
53. For syntheses of 4-deoxypodophyllotoxin, isopodophyllotoxin, 4-deoxyisopodophyllotoxin, and epiisopodophyllotoxin, see: (a) Hanessian, S.; Ninkovic, S. Can. J. Chem. 1996, 74, 1880-1888. (b) Kuroda, T.; Takahashi, M.; Kondo, K.; Iwasaki, T. J. Org. Chem. 1996, 61, 9560-9563. (c) Bogucki, D. E.; Charlton, J. L. J. Org. Chem. 1995, 60, 588-593. (d) Pelter, A.; Ward, R. S.; Qianrong, L.; Pis, J. Tetrahedron: Asymmetry 1994, 5, 909-920. (e) Itoh, T.; Chika, J.-I.; Takagi, Y.; Nishiyama, S. J. Org. Chem. 1993, 58, 5717-5723. (f) Morimoto, T.; Chiba, M.; Achiwa, K. Tetrahedron 1993, 49, 1793-1806 (g) Choy, W. Tetrahedron 1990, 46, 2281-2286.
54. For syntheses of 4-deoxypodophyllotoxin, isopodophyllotoxin, 4-deoxyisopodophyllotoxin, and epiisopodophyllotoxin, see: (a) Hanessian, S.; Ninkovic, S. Can. J. Chem. 1996, 74, 1880-1888. (b) Kuroda, T.; Takahashi, M.; Kondo, K.; Iwasaki, T. J. Org. Chem. 1996, 61, 9560-9563. (c) Bogucki, D. E.; Charlton, J. L. J. Org. Chem. 1995, 60, 588-593. (d) Pelter, A.; Ward, R. S.; Qianrong, L.; Pis, J. Tetrahedron: Asymmetry 1994, 5, 909-920. (e) Itoh, T.; Chika, J.-I.; Takagi, Y.; Nishiyama, S. J. Org. Chem. 1993, 58, 5717-5723. (f) Morimoto, T.; Chiba, M.; Achiwa, K. Tetrahedron 1993, 49, 1793-1806 (g) Choy, W. Tetrahedron 1990, 46, 2281-2286.
55. Berkowitz, D. B.; Maeng, J.-H.; Dantzig, A. H., Shepard, R. L., Norman, B. H. J. Am. Chem. Soc. 1996, 118, 9426-9427.
56. For discussions of chemoenzymatic natural product synthesis, see: (a) Hudlicky, T.; Tian, X.; Königsberger, K.; Maurya, R.; Rouden, J.; Fan, B. J. Am. Chem. Soc. 1996, 118, 10752-10765. (b) Johnson, C. R. Tetrahedron 1996, 52, 3769-3826. (c) Mori, K. Synlett 1995, 1097- 1109.
57. For discussions of chemoenzymatic natural product synthesis, see: (a) Hudlicky, T.; Tian, X.; Königsberger, K.; Maurya, R.; Rouden, J.; Fan, B. J. Am. Chem. Soc. 1996, 118, 10752-10765. (b) Johnson, C. R. Tetrahedron 1996, 52, 3769-3826. (c) Mori, K. Synlett 1995, 1097- 1109.
58. For discussions of chemoenzymatic natural product synthesis, see: (a) Hudlicky, T.; Tian, X.; Königsberger, K.; Maurya, R.; Rouden, J.; Fan, B. J. Am. Chem. Soc. 1996, 118, 10752-10765. (b) Johnson, C. R. Tetrahedron 1996, 52, 3769-3826. (c) Mori, K. Synlett 1995, 1097-1109.
59. (a) Ishibashi, H.; Ito, K.; Hirano, T.; Tabuchi, M.; Ikeda, M. Tetrahedron 1993, 49, 4173-4182.
60. (b) O'Connor, B.; Zhang, Y.; Negishi, E.-I.; Luo, F.-T.; Cheng, J.-W. Tetrahedron Lett. 1988, 29, 3903-3906.
61. For examples of retro-Michael cycloreversions in oxabicyclo-[2.2.1]heptyl systems bearing an acidic hydrogen a to the bridgehead, see: (a) Keay, B. A.; Rajapaksa, D.; Rodrigo, R. Can. J. Chem. 1984, 62, 1093-1098. (b) Keay, B. A.; Rodrigo, R. Tetrahedron 1984, 40, 4597-4607.
62. For examples of retro-Michael cycloreversions in oxabicyclo- [2.2.1]heptyl systems bearing an acidic hydrogen a to the bridgehead, see: (a) Keay, B. A.; Rajapaksa, D.; Rodrigo, R. Can. J. Chem. 1984, 62, 1093-1098. (b) Keay, B. A.; Rodrigo, R. Tetrahedron 1984, 40, 4597-4607.
63. This is to be contrasted with "sterically protected" IBFs such as 1,3-diphenyl-IBF that are much more easily handled yet reactive enough to trap alkenes with short lifetimes. For examples, see: Friedrichsen, W. Adv. Hetereocycl. Chem. 1980, 26, 135-241.
64. For a review of the use of isobenzofurans in natural product synthesis, see: Rodrigo, R. Tetrahedron 1988, 44, 2093-2135.
65. Both acid- and base-catalyzed 1,4-elimination of alkoxydihydroisobenzofurans to the corresponding isobenzofurans are well-known: Tobia, D.; Rickborn, B. J. Org. Chem. 1987, 52, 2611-2615.
66. Bromination (84% yield): (a) Conrad, P. C.; Kwiatkowski, P. L.; Fuchs, P. L. J. Org. Chem. 1987, 52, 586-591. Acetalization (96% yield): (b) Keay, B. A.; Plaumann, H. P.; Rajapaksa, D., Rodrigo, R. Can J. Chem. 1983, 61, 1987-1995.
67. Bromination (84% yield): (a) Conrad, P. C.; Kwiatkowski, P. L.; Fuchs, P. L. J. Org. Chem. 1987, 52, 586-591. Acetalization (96% yield): (b) Keay, B. A.; Plaumann, H. P.; Rajapaksa, D., Rodrigo, R. Can J. Chem. 1983, 61, 1987-1995.
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88. The corresponding acid is commercially available, making this a convenient model system.
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