Expeditious and Divergent Total Syntheses of Aspidosperma Alkaloids Exploiting Iridium(I)-Catalyzed Generation of Reactive Enamine Intermediates

Angewandte Chemie - International Edition

Volumn 55, Issue 43, 2016, Pages 13436-13440

  Tan, Peng Wen ^a,b   Seayad, Jayasree ^b   Dixon, Darren J ^a  

^a UNIVERSITY OF OXFORD   (United Kingdom)

^b INSTITUTE OF CHEMICAL AND ENGINEERING SCIENCES   (Singapore)

Author keywords

aspidosperma alkaloid; enamine; iridium catalyzed reduction; lactam; total synthesis

Indexed keywords

ADDITION REACTIONS; ALKALOIDS; AMIDES; CATALYSIS; POLYCYCLIC AROMATIC HYDROCARBONS; SYNTHESIS (CHEMICAL);

ASPIDOSPERMA; DIASTEREOSELECTIVITIES; ENAMINE INTERMEDIATES; ENAMINES; LACTAM; PRODUCT SELECTIVITIES; REDUCTIVE CYCLIZATION; TOTAL SYNTHESIS;

IRIDIUM COMPOUNDS;

ALKALOID; AMINE; IRIDIUM;

ASPIDOSPERMA; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; CYCLOADDITION; SYNTHESIS;

ALKALOIDS; AMINES; ASPIDOSPERMA; CATALYSIS; CYCLOADDITION REACTION; IRIDIUM; MOLECULAR STRUCTURE;

EID: 84988807832     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201605503     Document Type: Article

References (72)

1. S. E. Malawista, H. Sato, K. G. Bensch, Science 1968, 160, 770;
2. R. I. Owellen, C. A. Hartke, R. M. Dickerson, F. O. Haines, Cancer Res. 1976, 36, 1499;
3. H. L. Pearce in The Alkaloids, Vol. 37 (Eds.: A. Brossi, M. Suffness), Academic Press, San Diego, 1990, p. 145;
4. B. Gigant, C. G. Wang, R. B. G. Ravelli, F. Roussi, M. O. Steinmetz, P. A. Curmi, A. Sobel, M. Knossow, Nature 2005, 435, 519;
5. “The Vinca Alkaloids”: F. Gueritte, J. Fahy in Anticancer Agents from Natural Products (Eds.: D. J. C. Newman, G. M. Kingston), Taylor & Francis, New York, 2005.
6. Selected examples:
7. J. P. Kutney, U. Bunzlitrepp, K. K. Chan, J. P. D. Souza, Y. Fujise, T. Honda, J. Katsube, F. K. Klein, A. Leutwiler, S. Morehead, M. Rohr, B. R. Worth, J. Am. Chem. Soc. 1978, 100, 4220;
8. S. Yokoshima, T. Ueda, S. Kobayashi, A. Sato, T. Kuboyama, H. Tokuyama, T. Fukuyama, J. Am. Chem. Soc. 2002, 124, 2137;
9. S. A. Kozmin, T. Iwama, Y. Huang, V. H. Rawal, J. Am. Chem. Soc. 2002, 124, 4628;
10. H. Ishikawa, G. I. Elliott, J. Velcicky, Y. Choi, D. L. Boger, J. Am. Chem. Soc. 2006, 128, 10596;
11. I. Coldham, A. J. M. Burrell, L. E. White, H. Adams, N. Oram, Angew. Chem. Int. Ed. 2007, 46, 6159;
12. Angew. Chem. 2007, 119, 6271;
13. E. S. Sattely, S. J. Meek, S. J. Malcolmson, R. R. Schrock, A. H. Hoveyda, J. Am. Chem. Soc. 2009, 131, 943;
14. F. De Simone, J. Gertsch, J. Waser, Angew. Chem. Int. Ed. 2010, 49, 5767;
15. Angew. Chem. 2010, 122, 5903;
16. D. Kato, Y. Sasaki, D. L. Boger, J. Am. Chem. Soc. 2010, 132, 3685;
17. L. McMurray, E. M. Beck, M. J. Gaunt, Angew. Chem. Int. Ed. 2012, 51, 9288;
18. Angew. Chem. 2012, 124, 9422;
19. R. Frei, D. Staedler, A. Raja, R. Franke, F. Sasse, S. Gerber-Lemaire, J. Waser, Angew. Chem. Int. Ed. 2013, 52, 13373;
20. Angew. Chem. 2013, 125, 13615;
21. R. Yang, F. G. Qiu, Angew. Chem. Int. Ed. 2013, 52, 6015;
22. Angew. Chem. 2013, 125, 6131;
23. X.-L. Shen, R.-R. Zhao, M.-J. Mo, F.-Z. Peng, H.-B. Zhang, Z.-H. Shao, J. Org. Chem. 2014, 79, 2473.
24. O. Wagnières, Z. Xu, Q. Wang, J. Zhu, J. Am. Chem. Soc. 2014, 136, 15102.
25. H. Mizoguchi, H. Oikawa, H. Oguri, Nat. Chem. 2014, 6, 57.
26. M. Mewald, J. W. Medley, M. Movassaghi, Angew. Chem. Int. Ed. 2014, 53, 11634;
27. Angew. Chem. 2014, 126, 11818.
28. S. B. Jones, B. Simmons, A. Mastracchio, D. W. C. Macmillan, Nature 2011, 475, 183.
29. A. W. Gregory, A. Chambers, A. Hawkins, P. Jakubec, D. J. Dixon, Chem. Eur. J. 2015, 21, 111.
30. Y. Motoyama, M. Aoki, N. Takaoka, R. Aoto, H. Nagashima, Chem. Commun. 2009, 1574.
31. Selected reviews:
32. M. E. Kuehne, Synthesis 1970, 510;
33. P. W. Hickmott, Tetrahedron 1982, 38, 1975;
34. nd ed., Marcel Dekker, New York, 1988.
35. E. Wenkert, J. Am. Chem. Soc. 1962, 84, 98;
36. A. A. Qureshi, A. I. Scott, Chem. Commun. 1968, 947;
37. A. I. Scott, Bioorg. Chem. 1974, 3, 398.
38. F. E. Ziegler, E. B. Spitzner, J. Am. Chem. Soc. 1973, 95, 7146;
39. M. E. Kuehne, T. H. Matsko, J. C. Bohnert, C. L. Kirkemo, J. Org. Chem. 1979, 44, 1063;
40. M. E. Kuehne, D. M. Roland, R. Hafter, J. Org. Chem. 1978, 43, 3705;
41. M. E. Kuehne, J. A. Huebner, T. H. Matsko, J. Org. Chem. 1979, 44, 2477;
42. M. E. Kuehne, J. C. Bohnert, J. Org. Chem. 1981, 46, 3443;
43. M. E. Kuehne, F. J. Okuniewicz, C. L. Kirkemo, J. C. Bohnert, J. Org. Chem. 1982, 47, 1335;
44. M. E. Kuehne, D. E. Podhorez, J. Org. Chem. 1985, 50, 924;
45. M.-C. Barsi, B. C. Das, J.-L. Fourrey, R. Sundaramoorthi, J. Chem. Soc. Chem. Commun. 1985, 88;
46. G. Kalaus, M. Kiss, M. Kajtar-Peredy, J. Brlick, L. Szabo, C. Szantay, Heterocycles 1985, 23, 2783;
47. J. P. Brennan, J. E. Saxton, Tetrahedron 1986, 42, 6719;
48. S. Jegham, J.-L. Fourrey, B. C. Das, Tetrahedron Lett. 1989, 30, 1959;
49. S. Kobayashi, G. Peng, T. Fukuyama, Tetrahedron Lett. 1999, 40, 1519;
50. S. Kobayashi, T. Ueda, T. Fukuyama, Synlett 2000, 883;
51. S. Yokoshima, T. Ueda, S. Kobayashi, A. Sato, T. Kuboyama, H. Tokuyama, T. Fukuyama, J. Am. Chem. Soc. 2002, 124, 2137;
52. Y. Han-ya, H. Tokuyama, T. Fukuyama, Angew. Chem. Int. Ed. 2011, 50, 4884;
53. Angew. Chem. 2011, 123, 4986.
54. N. Kornblum, J. W. Powers, G. J. Anderson, W. J. Jones, H. O. Larson, O. Levand, W. M. Weaver, J. Am. Chem. Soc. 1957, 79, 6562;
55. N. Kornblum, W. J. Jones, G. J. Anderson, J. Am. Chem. Soc. 1959, 81, 4113;
56. P. Dave, H.-S. Byun, R. Engel, Synth. Commun. 1986, 16, 1343.
57. Selected examples on the application of Fischer indole synthesis in total synthesis:
58. J. Bonjoch, J. Catena, N. Valls, J. Org. Chem. 1996, 61, 7106;
59. R. Iyengar, K. Schildknegt, J. Aube, Org. Lett. 2000, 2, 1625;
60. C. W. Roberson, K. A. Woerpel, J. Am. Chem. Soc. 2002, 124, 11342;
61. T. Gan, R. Liu, P. Yu, S. Zhao, J. M. Cook, J. Org. Chem. 1997, 62, 9298.
62. L. Furst, B. S. Matsuura, J. M. R. Narayanam, J. W. Tucker, C. R. J. Stephenson, Org. Lett. 2010, 12, 3104.
63. R. Kuwano, M. Takahashi, Y. Ito, Tetrahedron Lett. 1998, 39, 1017.
64. Concerted Diels–Alder reaction pathway cannot be ruled at this stage of investigation.
65. Selected examples on silica gel promoted reactions:
66. Q. Ding, B. Cao, Z. Zong, Y. Peng, J. Comb. Chem. 2010, 12, 370;
67. C.-Y. Ho, S. Roy, Y.-M. Chen, K. Chen, J. Chin. Chem. Soc. 2012, 59, 940;
68. Y. Zhou, C.-X. Zhuo, Q. Gu, S.-L. You, Adv. Synth. Catal. 2015, 357, 912;
69. A. Sagar, V. N. Babu, D. S. Sharada, RSC Adv. 2015, 5, 29066;
70. Y.-H. Zhang, M.-Y. Wu, W.-C. Huang, RSC Adv. 2015, 5, 105825.
71. J. P. Kutney, C. Ehret, V. R. Nelson, D. C. Wigfield, J. Am. Chem. Soc. 1968, 90, 5929.
72. The N-Boc protected lactam derivative 18 was subjected to the same Ir-catalyzed reduction conditions (see the Supporting Information for details). In this case only 13 % of reductive cyclization product 22 was obtained; the remainder of the mass was largely over-reduced lactam and importantly no formal Diels–Alder product was observed.