Highly diastereoselective samarium diiodide induced ketyl cyclisations of indole and pyrrole derivatives - Scope and limitations

European Journal of Organic Chemistry

Volumn , Issue 14, 2010, Pages 2716-2732

  Beemelmanns, Christine ^a   Blot, Virginie ^a,b   Gross, Steffen ^a,c   Lentz, Dieter ^a   Reissig, Hans Ulrich ^a  

^a FREIE UNIVERSITÄT BERLIN   (Germany)

^b UNIVERSITÉ DE NANTES   (France)

^c BASF SE   (Germany)

Author keywords

Cyclization; Indoles; Ketyl coupling; Nitrogen heterocycles; Pyrroles; Radical reactions; Samarium diiodide

Indexed keywords

EID: 77951876242     PISSN: 1434193X     EISSN: 10990690     Source Type: Journal    
DOI: 10.1002/ejoc.200901455     Document Type: Article

References (119)

1. a) J.-L. Namy, H. B. Kagan, Now. J. Chim. 1977, 1, 5-7;
2. b) P. Girard, J.-L. Namy, H. B. Kagan, J. Am. Chem. Soc. 1980, 102, 2693-2698.
3. 2-promoted reactions: a) G. A. Molander, C. R. Harris, Chem. Rev. 1996, 96, 307-338;
4. b) F. A. Khan, R. Zimmer, J. Prakt. Chem. 1997, 339, 101-104;
5. c) G. A. Molander, C. R. Harris, Tetrahedron 1998, 54, 3321-3354;
6. d) A. Krief, A.-M. Laval, Chem. Rev. 1999, 99, 745-777;
7. e) H. B. Kagan, Tetrahedron 2003, 59, 10351-10372;
8. f) M. Bemdt, S. Gross, A. Hölemann, H.-U. Reissig, Synlett 2004, 422-438;
9. g) D. J. Edmonds, D. Johnston, D. J. Procter, Chem. Rev. 2004, 104, 3371-3404;
10. h) K. Gopalaiah, H. B. Kagan, New J. Chem. 2008, 32, 607-637;
11. i) I. M. Rudkin, L. C. Miller, D. J. Procter, Organomet. Chem. 2008, 34, 19-45;
12. j) K. C. Nicolaou, S. P. Ellery, J. S. Chen, Angew. Chem. 2009, 121, 7276-7301;
13. Angew. Chem. Int. Ed. 2009, 48, 7140-7165;
14. k) D. J. Procter, R. A. Flowers II in Organic Synthesis by Using Samarium Diiodide, Royal Society of Chemistry, Cambridge, 2009.
15. For the formation of medium-sized carbocycles and heterocycles through intramolecular samarium ketyl additions to alkene and alkyne units, see: a) F. A. Khan, R. Czerwonka, R. Zimmer, H.-U. Reissig, Synlett 1997, 995-997;
16. b) E. Nandanan, C. U. Dinesh, H.-U. Reissig, Tetrahedron 2000, 56, 4267-4277
17. c) A. Hölemann, H.-U. Reissig, Synlett 2004, 2732-2735;
18. d) H.-U. Reissig, F. A. Khan, R. Czerwonka, C. U. Dinesh, A. L. Shaikh, R. Zimmer, Eur. J. Org. Chem. 2006, 4419-4428;
19. e) J. Saadi, D. Lentz, H.-U. Reissig, Org. Lett. 2009, 11, 3334-3337;
20. i) J. Saadi, H.-U. Reissig, Synlett 2009, 2089-2092; and literature cited therein.
21. For the intramolecular additions of samarium ketyl to aryl groups, see: a) C. U Dinesh, H.-U. Reissig, Angew. Chem. 1999, 111, 874-876;
22. Angew. Chem. Int. Ed. 1999, 38, 789-791;
23. b) M. Berndt, I. Hlobilová, H.-U. Reissig, Org. Lett. 2004, 6, 957-960;
24. c) F. Aulenta, M. Berndt, I. Brüdgam, H. Hartl, S. Sörgel, H.-U. Reissig, Chem. Eur. J. 2007, 13, 6047-6062;
25. d) U. K. Wefelscheid, M. Berndt, H.-U. Reissig, Eur. J. Org. Chem. 2008, 3635-3646;
26. e) U. K. Wefelscheid, H.-U Reissig, Adv. Synth. Catal. 2008, 350, 65-69.
27. 2-promoted aryl-carbonyl couplings, see: a) H.-G. Schmalz, S. Siegel, J. W. Bats, Angew. Chem. 1995, 107, 2597-2599;
28. Angew. Chem. Int. Ed. Engl. 1995, 34, 2383-2385;
29. b) J.-S. Shiue, M.-H. Lin, J.-M. Fang, J. Org. Chem. 1997, 62, 4643-4649;
30. c) C.-W. Kuo, J.-M. Fang, Synth. Commun. 2001, 31, 877-892;
31. d) H. Ohno, S. Maeda, M. Okumura, R. Wakayama, T. Tanaka, Chem. Commun. 2002, 316-317;
32. e) H. Ohno, R. Wakayama, S. Maeda, H. Iwasaki, M. Okumura, C. Iwata, H. Mikamiyama, T. Tanaka, J. Org. Chem. 2003, 68, 5909-5916;
33. f) H. Ohno, M. Okumura, S. Maeda, H. Iwasaki, R. Wakayama, T. Tanaka, J. Org. Chem. 2003, 68, 7722-7732.
34. For the intramolecular additions of samarium ketyl to aniline derivatives, see: a) S. Gross, H.-U. Reissig, Synlett 2002, 2027-2030;
35. b) R. S. Kumaran, I. Brüdgam, H.-U. Reissig, Synlett 2008, 991 994.
36. Reviews dealing with synthetic applications of dearomatising processes: for reductive dearomatisations, see: a) L. N. Mander, Synlett 1991, 134-144;
37. b) T. J. Donohoe, R. Garg, C. A. Stevenson, Tetrahedron: Asymmetry 1996, 7, 317-344;
38. c) A. Schultz, Chem. Comtnun. 1999, 1263-1271; for nucleophilic dearomatisations, see:
39. d) J. Clayden, M. N Kenworthy, Synthesis 2004, 1721-1736;
40. e) F. López-Ortiz, M.J. Iglesias, I. Fernández, C. M. A. Sánchez, G. R. Gómez, Chem. Rev. 2007, 107, 1580-1691;
41. f) G. Barbe, G. Pelletier, A. B. Charette, Org. Lett. 2009, 11, 3398-3401; for transition-metal-mediated dearomatisations, see:
42. g) T. Bach, Angew. Chem. 1996, 105, 795-796;
43. Angew. Chem. Int. Ed. Engl. 1996, 35, 729-730;
44. h) A. R. Pape, K. P. Kaliappan, E. P. Kündig, Chem. Rev. 2000, 100, 2917-2940; for oxidative dearomatisations, see:
45. i) S. Quideau, L. Pouységu, D. Deffieux, Synlett 2008, 467-495; and references cited therein.
46. For selected reviews on indole synthesis and indole-containing natural products, see: a) R. J. Sundberg in The Chemistry of Indoles, Academic Press, New York, 1970;
47. b) R. J. Sundberg in Indoles, Academic Press, London, 1996;
48. c) J. Bonjoch, J. Bosch, in: The Alkaloids, vol.48 (Ed.: G. A. Cordell), Academic Press, San Diego, 1996, pp. 75-189;
49. d) G. W. Gribble, J. Chem. Soc. Perkin Trans. 1 2000, 1045-1075;
50. e) J. Bonjoch, D. Solé, Chem. Rev. 2000, 100, 3455-3482;
51. f) M. Somei, F. Yamada, Nat. Prod. Rep. 2005, 22, 73-103;
52. g) G. R. Humphrey, T. Kuethe, Chem. Rev. 2006, 106, 2875-2911;
53. h) K. Higuchi, T. Kawasaki, Nat. Prod. Rep. 2007, 24, 843-868; for selected reviews dealing with indolizidines
54. i) A. S. Howard, J. P. Michael, in The Alkaloids, vol.28 (Ed.: A. Brossi), Academic Press, New York, 1986, pp. 183-308;
55. j) A. D. Elbein, R. J. Molyneux, in Alkaloids: Chemical and Biological Perspectives, vol.5 (Ed.: S.W. Pelletier), Wiley, New York, 1987, pp. 1-54;
56. k) R. Ben-Othman, M. Othman, K. Ciamala, M. Knorr, C. Strohmann, B. Decroix, Tetrahedron 2009, 65, 4846-4854; for selected reviews on pyrrolidine derivatives, see:
57. C. Christophersen, in: The Alkaloids, vol.24 (Ed.: A. Brossi), Academic Press, Orlando, 1985, pp. 25-98;
58. m) D. J. Robins, Nat. Prod. Rep. 1995, 12, 413-418;
59. n) J. R. Liddell, Nat. Prod, Rep. 2000, 17, 455-462;
60. o) S. Agarwal, S. Cämmerer, S. Filali, W. Fröhner, J. Knöll, M. P. Krahl, K. R. Reddy, H.-J. Knölker, Curr. Org. Chem. 2005, 9, 1601-1614;
61. p) A. Brandi, F. Cardona, S. Cicchi, F. M. Cordero, A. Goti, Chem. Eur. J. 2009, 15, 7808-7821; and literature cited therein.
62. a) S. Gross, H.-U. Reissig, Org. Lett. 2003, 5, 4305-4307;
63. b) S. Gross, Dissertation, Freie Universität Berlin, 2003;
64. c) V. Blot, H.-U. Reissig, Eur. J. Org. Chem. 2006, 4989-4992;
65. d) V. Blot, H.-U. Reissig, Synlett 2006, 2763-2766;
66. e) C. Beemelmanns, H.-U. Reissig, Org. Biomol. Chem. 2009, 7, 4475-4480.
67. a) N Kise, T. Mano, T. Sakurai, Org. Lett. 2008, 10, 4617-4620;
68. [9a], we assume that the correct relative configuration of their obtained product is as depicted in Schemes 8, 10 and 11.
69. S. Würtz, S. Rakshit, I Neumann, T. Droge, F. Glorius, Angew. Chem. 2008, 120, 7340-7343;
70. Angew. Chem. Int. Ed. 2008, 47, 7230-7233.
71. For the preparation of 1-(2′,3′-dimethyl-1H-indol-1-yl) pentane-1,4-dione see the Supporting Information.
72. C. Iieathcock, T. W. Geldern, Heterocycles 1987, 25, 75-78.
73. A. Basha, M. Lipton, S. M. Weinreb, Tetrahedron Lett. 1977, 18, 4171-4174.
74. For the preparation of alkyl iodide 20 see the Supporting Information.
75. Selected publications for the role of HMPA, see: a) J. Inanaga, M. Ishikawa, M. Yamaguchi, Chem. Lett. 1987, 1485-1486;
76. b) Z. Hou, Y. Wakatsuki, J. Chem. Soc. Chem. Commun. 1994, 1205-1206;
77. c) E. Prasad, R. A. Flowers II, J. Am. Chem. Soc. 2002, 124, 6895-6899;
78. d) A. Dahlén, G. Hilmersson, Eur. J. Inorg. Chem. 2004, 3393-3403;
79. e) T. Inokuchi, J. Org. Chem. 2005, 70, 1497-1500;
80. f) R. A. Flowers II, Synlett 2008, 1427-1439;
81. g) D. V. Sadasivam, P. K. S. Antharjanam, E. Prasad, R. A. Flowers II, J. Am. Chem. Soc. 2008, 130, 7228-7229;
82. h) H. Farran, S. Hoz, Org. Lett. 2008, 10, 865-867.
83. R. Yanada, N. Negoro, K. Bessho, K. Yanada, Synlett 1995, 1261-1263.
84. a) A. L. J. Beckwith, Tetrahedron 1981, 37, 3073-3100;
85. b) D. C. Spellmeyer, K. N. Honk, J. Org. Chem. 1987, 52, 959-974.
86. [2g-2i]
87. For a similar reported mechanism, see: a) J.-S. Shiue, J.-M. Fang, J. Chem. Soc., Chem. Commun. 1993, 1277-1278;
88. b) S.-C. Lin, F.-D. Yang, J.-S. Shiue, S.-M. Yang, J.-M. Fang, J. Org. Chem. 1998, 63, 2909-2917.
89. It should be mentioned that in cyclohexane the A value of a methyl group is higher than the A value of a hydroxy group. For A values, see: a) N. L. Allinger, L. A. Freiberg, J. Org. Chem. 1966, 31, 894-897;
90. (2+/3+) ions are partially coordinated to the carbonyl group (in particular in the absence of HMPA). The complexed carbonyl group should thus prefer mainly an equatorial position.
91. [4d,5d-5fl
92. 2-mediated 4-exo-trig cyclisation, see: a) K. Weinges, S. B. Schmidbauer, H. Schick, Chem. Ber. 1994, 127, 1305- 1309;
93. b) D. Iohnston, C. M. McCusker, D. J. Procter, Tetrahedron Lett. 1999, 40, 4913-4916;
94. c) D. Iohnston, C. F. McCusker, K. Muir, D. J. Procter, J. Chem. Soc. Perkin Trans. 1 2000, 681-684;
95. d) T. K. Button, K. W. Muir, D. J. Procter, Org. Lett. 2003, 5, 4811-4814;
96. e) D. J. Edmonds, K. W. Muir, D. J. Procter, J. Org. Chem. 2003, 68, 3190-3198;
97. f) D. Bradley, G. Williams, K. Blann, Eur. J. Org. Chem. 2004, 3286-3291; for other metal-mediated radical 4-exo cyclisations, see, for example:
98. g) J. Friedrich, K. Walczak, M. Dolg, F. Piestert, T. Lauterbach, D. Worgull, A. Gansäuer, J. Am. Chem. Soc. 2008, 130, 1788-1796 and ref. cited therein.
99. 2-induced reactions, see: a) S. Hoz, A. Yacovan, I. Bilkis, J. Am. Chem. Soc. 1996, 118, 261-262;
100. b) A. Dahlén, G. Hilmersson, Tetrahedron Lett. 2001, 42, 5565-5569;
101. c) G. Kleinert, A. Tarnopolsky, S. Hoz, Org. Lett. 2005, 7, 4197-4200;
102. [16f,16h]
103. The earlier assumption of all-cis-configured products was due to COSY artefacts in the recorded NOESY spectra. These artefacts are particularly well known for substrates with large vicinal diaxial coupling constants, see: S. Macura, Y. Huang, D. Suter, R. R. Ernst, J. Magn. Reson. 1981, 43, 259-281.
104. For a recent review dealing with NMR-based structure elucidation, see: E. E. Kwon, S. G. Huang, Eur. J. Org. Chem. 2008, 2671-2688.
105. For the synthesis of the starting materials 37 and 39 see the Supporting Information.
106. a) M. Berndt, H.-U. Reissig, unpublished results;
107. b) M. Berndt, Dissertation, Freie Universität Berlin, 2003.
108. 2-induced cyclisations only afforded diastereomers of type II and the corresponding y-lactones.
109. ORTEP-3 for windows, L. I Farrugia, J. Appl. Crystallogr. 1997, 30, 565.
110. [2g,3d,4c,9c,9e] [31] Reductions to dihydroindole derivatives were only observed for sterically more demanding ketones, indicating that the reaction rate for the formation of the ketyl radical is decreasing significantly with steric demand.
111. For similar C-C bond cleavage, see: D. Bradley, G. Williams, K. Blann, C. W. Holzapfel, J. Org. Chem. 2000, 65, 2834-2836;
112. A. Schartz, C Seger, Monatsh. Chem. 2001, 132, 855-858;
113. [2g,9b] and ref. cited therein.
114. For related acyl radical cyclisations onto pyrroles, see: a) D. J. Hart in Radicals in Organic Synthesis, Vol.2 (Eds.: P. Renaud, M. P. Sibi), Wiley-VCH, Weinheim, 2001, pp. 279-300;
115. b) S. M. Allin, W. R. S. Barton, W. R. Bowman, T. McInally, Tetrahedron Lett. 2001, 42, 7887-7890;
116. c) M. Yoshida, M. Kitamura, K. Narasaka, Bull. Chem. Soc., Jpn. 2003, 76, 2003-2008; and ref. cited therein.
117. After HPLC purification of the reaction mixture compound 60 and an inseparable mixture of the minor diastereomers were isolated.
118. For a closely related alkylated substrate an X-ray analysis was obtained and will be reported in due course. D. Lentz, C Beemelmanns, H.-U. Reissig, Freie Universität Berlin, unpublished results.
119. SHELX97 - Programs for Crystal Structure Analysis (Release 97-2). G. M. Sheldrick, Institut für Anorganische Chemie der Universität, Tammanstrasse 4, 3400 Göttingen, Germany, 1998.