Enantioselective rhodium-catalyzed [2 + 2 + 2] cycloadditions of terminal alkynes and alkenyl isocyanates: Mechanistic insights lead to a unified model that rationalizes product selectivity

Journal of the American Chemical Society

Volumn 131, Issue 43, 2009, Pages 15717-15728

  Dalton, Derek M ^a   Oberg, Kevin M ^a   Yu, Robert T ^a   Lee, Ernest E ^a   Perreault, Stéphane ^a   Oinen, Mark Emil ^a   Pease, Melissa L ^a   Malik, Guillaume ^a   Rovis, Tomislav ^a  

^a Department of Environmental and Radiological Health Sciences   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

[2+2+2] CYCLOADDITION; ALIPHATIC ALKYNES; ALKENYL; BIPHENOL; CATALYTIC CYCLES; CYCLOADDITIONS; ENANTIO; ENANTIOSELECTIVE; PHOSPHORAMIDITE LIGANDS; PHOSPHORAMIDITES; PRODUCT SELECTIVITIES; RHODIUM-CATALYZED; TERMINAL ALKYNE; UNIFIED MODEL; X-RAY STRUCTURE;

ACETYLENE; CHLORINE COMPOUNDS; CYCLOADDITION; DIMERIZATION; LIGANDS; OLEFINS; RHODIUM;

RHODIUM COMPOUNDS;

ALKENE; ALKENYL GROUP; ALKYNE DERIVATIVE; CHLORIDE; INDOLIZIDINE ALKALOID; ISOCYANIC ACID DERIVATIVE; PHOSPHORAMIDIC ACID DERIVATIVE; QUINOLIZIDINE DERIVATIVE; RHODIUM;

ARTICLE; CATALYSIS; CYCLOADDITION; DIMERIZATION; DRUG ISOLATION; DRUG STRUCTURE; ENANTIOSELECTIVITY; SUBSTITUTION REACTION; X RAY;

ALKYNES; CATALYSIS; ISOCYANATES; RHODIUM; STEREOISOMERISM;

EID: 70350662862     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja905065j     Document Type: Article

References (100)

1. (a) Daly, J. W. J. Med. Chem. 2003, 46, 445-452.
2. (b) Daly, J. W.; Spande, T. F.; Garraffo, H. M. J. Nat. Prod. 2005, 68, 1556-1575.
3. For reviews of recent syntheses, see: (a) Michael, J. P. Nat. Prod. Rep. 2000, 17, 579-602.
4. (b) Michael, J. P. Nat. Prod. Rep. 2002, 20, 458-475.
5. (c) Michael, J. P. Nat. Prod. Rep. 2005, 22, 603-626.
6. (d) Michael, J. P. Nat. Prod. Rep. 2007, 24, 191-222.
7. (e) Michael, J. P. Nat. Prod. Rep. 2008, 25, 139-165.
8. For selected syntheses: (a) Kim, G.; Jung, S.-d.; Kim, W.-j. Org. Lett. 2001, 3, 2985-2987.
9. (b) Toyooka, N.; Fukutome, A.; Nemoto, H.; Daly, J. W.; Spande, T. F.; Garraffo, H. M.; Kaneko, T. Org. Lett. 2002, 4, 1715-1717.
10. (c) Hermet, J.-P. R.; McGrath, M. J.; O'Brien, P.; Porter, D. W.; Gilday, J. Chem. Commun. 2004, 1830-1831.
11. (d) Zaja, M.; Blechert, S. Tetrahedron 2004, 60, 9629-9634.
12. (e) Toyooka, N.; Kawasaki, M.; Nemoto, H.; Awale, S.; Tezuka, Y.; Kadota, S. Synlett 2005, 3109-3110.
13. (f) Toyooka, N.; Dejun, Z.; Nemoto, H.; Garraffo, H. M.; Spande, T. F.; Daly, J. W. Tetrahedron Lett. 2006,
14. For tandem conjugate additions, see: (a) Back, T. G.; Nakajima, K. J. Org. Chem. 1998, 63, 6566-6571.
15. (b) Ma, D.; Zhu, W. Org. Lett. 2001, 3, 3927-3929.
16. (c) Back, T. G.; Hamilton, M. D.; Lim, V. J. J.; Parvez, M. J. Org. Chem. 2005, 70, 967-972.
17. (d) Cai, G.; Zhu, W.; Ma, D. Tetrahedron 2006, 62, 5697-5708.
18. For cascade reactions, see: (a) Amorde, S. M.; Judd, A. S.; Martin, S. F. Org. Lett. 2005, 7, 2031-2033.
19. (b) Padwa, A.; Bur, S. K. Tetrahedron 2007, 63, 5341-5378.
20. For the use of dihydro-4-pyridones as synthons, see: (a) Joseph, S.; Comins, D. L. Curr. Opin. Drug Discovery Dev. 2002, 5, 870.
21. (b) Young, D. W.; Comins, D. L. Org. Lett. 2005, 7, 5661-5664.
22. For intramolecular Schmidt reaction, see: (a) Aubé, J.; Milligan, G. L. J. Am. Chem. Soc. 1991, 113, 8965-8966.
23. (b) Gracis, V.; Zeng, Y.; Desai, P.; Aubé, J. Org. Lett. 2003, 5, 4999-5001.
24. For a three component coupling using silyl dithianes, see: (a) Smith, A. B., III; Kim, D.-S. Org. Lett. 2004, 6, 1493-1495.
25. (b) Smith, A. B., III; Kim, D.-S. J. Org. Chem. 2006, 71, 2547-2557.
26. For a catalytic, asymmetric aza-Diels-Alder reaction, see: (a) García- Mancheño, O.; Gómez-Arrayás, R.; Carretero, J. C. J. Am. Chem. Soc. 2004, 126, 456-457.
27. (b) García-Mancheño, O.; Gómez-Arrayás, R.; Adrio, J.; Carretero, J. C. J. Org. Chem. 2007, 72, 10294-10297.
28. For reviews on [2 + 2 + 2] cycloadditions of alkynes see: (a) Saito, S.; Yamamoto, Y. Chem. Rev. 2000, 100, 2901-2915.
29. (b) Agenet, N.; Busine, O.; Slowinski, F.; Gandon, V.; Aubert, C.; Malacria, M. Org. React. 2007, 68, 1-302.
30. (c) Galan, B. R.; Rovis, T. Angew. Chem., Int. Ed. 2009, 48, 2830-2834.
31. For reviews on [2 + 2 + 2] cycloadditions of alkynes and nitrogen moieties see: (d) Varela, J. A.; Saá, C. Chem. Rev. 2003, 103, 3787-3801.
32. (e) Heller, B.; Hapke, M. Chem. Soc. Rev. 2007, 36, 1085-1094.
33. (f) Chopade, P. R.; Louie, J. Adv. Synth. Catal. 2006, 348, 2307-2327.
34. Ozaki, S. Chem. Rev. 1972, 72, 457-496.
35. Braunstein, P.; Nobel, D. Chem. Rev. 1989, 89, 1927-1945.
36. (a) Hong, P.; Yamazaki, H. Synthesis 1977, 1, 50-52.
37. (b) Hong, H.; Yamazaki, H. Tetrahedron Lett. 1977, 15, 1333-1336.
38. (c) Hoberg, H.; Oster, B. W. Synthesis 1982, 324-325.
39. (d) Hoberg, H.; Oster, B. W. J. Organomet. Chem. 1983, 234, C35-C38.
40. (e) Hoberg, H.; Oster, B. W. J. Organomet. Chem. 1983, 252, 359-364.
41. (a) Earl, R. A.; Vollhardt, K. P. C. J. Am. Chem. Soc. 1983, 105, 6991-6993.
42. (b) Earl, R. A.; Vollhardt, K. P. C. J. Org. Chem. 1984, 49, 4786-4800.
43. Cobalt: (a) Diversi, P.; Ingrosso, G.; Lucherini, A.; Malquori, S. J. Mol. Catal. 1987, 40, 267-280.
44. (b) Bonaga, L. V. R.; Zhang, H.-C.; Moretto, A. F.; Ye, H.; Gauthier, D. A.; Li, J.; Leo, G. C.; Maryanoff, B. E. J. Am. Chem. Soc. 2005, 127, 3473-3485.
45. Nickel: (c) Takahashi, T.; Tsai, F.; Li, Y.; Wang, H.; Kondo, Y.; Yamanaka, M.; Nakajima, K.; Kotora, M. J. Am. Chem. Soc. 2002, 124, 5059-5067.
46. (d) Duong, H. A.; Cross, M. J.; Louie, J. J. Am. Chem. Soc. 2004, 126, 11438-11439.
47. (e) Duong, H. A.; Louie, J. J. Organomet. Chem. 2005, 690, 5098-5104.
48. (f) Duong, H. A.; Louie, J. Tetrahedron 2006, 62, 7552-7559.
49. Ruthenium: (g) Yamamoto, Y.; Takagishi, H.; Itoh, K. Org. Lett. 2001, 3, 2117-2119.
50. (h) Yamamoto, Y.; Kinpara, K.; Saigoku, T.; Takagishi, H.; Okuda, S.; Nishiyama, H.; Itoh, K. J. Am. Chem. Soc. 2005, 127, 605-613.
51. Rhodium: (i) Flynn, S. T.; Hasso-Henderson, S. E.; Parkins, A. W. J. Mol. Catal. 1985, 32, 101-105.
52. (k) Kondo, T.; Nomura, M.; Ura, Y.; Wada, K.; Mitsudo, T. Tetrahedron Lett. 2006, 47, 7107-7111.
53. (a) Tanaka, K.; Wada, A.; Noguchi, K. Org. Lett. 2005, 7, 4737- 4739.
54. (b) Tanaka, K. Synlett 2007, 1977-1993.
55. (c) Tanaka, K.; Takahashi, Y.; Suda, T.; Hirano, M. Synlett 2008, 1724-1728.
56. (a) Yu, R. T.; Rovis, T. J. Am. Chem. Soc. 2006, 128, 2782-2783.
57. (b) Yu, R. T.; Rovis, T. J. Am. Chem. Soc. 2006, 128, 12370-12371.
58. (c) Lee, E. E.; Rovis, T. Org. Lett. 2008, 10, 1231-1234.
59. (d) Yu, R. T.; Rovis, T. J. Am. Chem. Soc. 2008, 130, 3262-3263.
60. (e) Yu, R. T.; Lee, E. E.; Malik, G.; Rovis, T. Angew. Chem., Int. Ed. 2009, 48, 2379-2382.
61. (f) Keller Friedman, R.; Rovis, T. J. Am. Chem. Soc. 2009, 131, 10775-10782.
62. (a) Albano, P.; Aresta, M. J. Organomet. Chem. 1980, 190, 243-246.
63. (b) Schäfer, H.; Marcy, R.; Rüping, T.; Singer, H. J. Organomet. Chem. 1982, 240, 17-25.
64. (c) Ohshita, J.; Furumori, K.; Matsuguchi, A.; Ishikawa, M. J. Org. Chem. 1990, 55, 3277-3280.
65. Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165.
66. TMS-acetylene does not participate under these reaction conditions.
67. During this study, we found that catalyst loading could be reduced from 10 to 5 mol % without sacrificing yield or enantioselectivity.
68. Hall, H. K. J. Am. Chem. Soc. 1957, 79, 5441.
69. Indolizidine (-)-209D is a non-natural indolizidine derived from the misassignment of pyrrolizidine 209-K; see ref 1b.
70. For selected publications with similar metallacycles involving an isocyanate and alkyne see: (a) Hoberg, H. J. Organomet. Chem. 1988, 358 (1-3), 507-517.
71. (b) Duong, H. A.; Louie, J. J. Organomet. Chem. 2005, 690 (23), 5098-5104.
72. (c) Louie, J. Curr. Org. Chem. 2005, 9 (7), 605-623.
73. (d) Yamamoto, Y.; Kinpara, K.; Saigoku, T.; Takagishi, H.; Okuda, S.; Nishiyama, H.; Itoh, K. J. Am. Chem. Soc. 2005, 127, 605-613.
74. (e) Kondo, T.; Nomura, M.; Ura, Y.; Wada, K.; Mitsudo, T. Tetrahedron Lett. 2006, 47 (39), 7107-7111.
75. (f) Duong, H. A.; Louie, J. Tetrahedron 2006, 62 (32), 7552-7559.
76. (g) Kondo, T.; Nomura, M.; Ura, Y.; Wada, K.; Mitsudo, T.-a. J. Am. Chem. Soc. 2006, 128, 14816-14817.
77. For selected CO migration references on rhodium(III) species see: (a) Cavallo, L.; Sola, M. J. Am. Chem. Soc. 2001, 123, 12294-12302.
78. (b) Gonsalvi, L.; Adams, H.; Sunley, G. J.; Ditzel, E.; Haynes, A. J. Am. Chem. Soc. 2002, 124, 13597-13612.
79. (c) Gonsalvi, L. Organometallics 2003, 22, 1047-1054, 5.
80. Oberg, K. M.; Lee, E. E.; Rovis, T. Tetrahedron 2009, 65, 5056-5061.
81. For a study of the effect of olefin substitution on the thermodynamics of alkene-nickel coordination, see: Tolman, C. A. J. Am. Chem. Soc. 1974, 96, 2780-2789.
82. A mechanism where the alkyne and alkene oxidatively cyclize to make a rhodacyclopentene followed by isocyanate insertion can be proposed, but this is unlikely because there is no plausible pathway to vinylogous amide and 4-pyridone. For computations proposing alkyne-alkyne cyclization followed by CdN insertion, see: (a) Schmid, R.; Kirchner, K. J. Org. Chem. 2003, 68, 8339-8344.
83. (b) Dazinger, G.; Schmid, R.; Kirchner, K. New J. Chem. 2004, 28, 153-155.
84. (c) Dazinger, G.; Torres-Rodrigues, M.; Kirchner, K.; Calhorda, M. J.; Costa, P. J. J. Organomet. Chem. 2006, 691, 4434-4445.
85. For complete details of the rhodium/phosphoramidite X-ray crystal analysis, see the Supporting Information.
86. For publications of rhodium and iridium phosphoramidite crystal structures see: (a) Bartels, B.; García-Yebra, C.; Rominger, F.; Helmchen, G. Eur. J. Inorg. Chem. 2002, 2569-2586.
87. (b) Leitner, A.; Shekhar, S.; Pouy, M. J.; Hartwig, J. F. J. Am. Chem. Soc. 2005, 127, 15506-15514.
88. (c) Faller, J. W.; Milheiro, S. C.; Parr, J. J. Organomet. Chem. 2006, 691, 4945-4955.
89. (d) Giacomina, F.; Meetsma, A.; Panella, L.; Lefort, L.; de Vries, A. H. M.; de Vries, J. G. Angew. Chem., Int. Ed. 2007, 46, 1497-1500.
90. (e) Mikhel, I. S.; Ruegger, H.; Butti, P.; Camponovo, F.; Huber, D.; Mezzetti, A. Organometallics 2008, 27, 2937-2948.
91. (f) Filipuzzi, S.; Maennel, E.; Pregosin, P. S.; Albinati, A.; Rizzato, S.; Veiros, L. F. Organometallics 2008, 27, 4580-4588.
92. Imabayashi, T.; Fujiwara, Y.; Nakao, Y.; Sato, H.; Sakaki, S. Organometallics 2005, 24, 2129-2140.
93. Wakatsuki, Y.; Nomura, O.; Kitaura, K.; Morokuma, K.; Yamazaki, H. J. Am. Chem. Soc. 1983, 105, 1907-1912.
94. For crystal structures, see: (a) Davies, G. R.; Hewerston, W. H.; Maise, R. H. B.; Owston, P. G.; Patel, C. G. J. Chem. Soc. 1970, 1873.
95. (b) Beauchamp, A. L.; Rochon, F. R.; Theophanides, T. Can. J. Chem. 1973, 51, 126.
96. For computational analysis of alkyne coordination to Pd, see: (c) de Vaal, P.; Dedieu, A. J. Organomet. Chem. 1994, 478, 121-129.
97. Stockis, A.; Hoffmann, R. J. Am. Chem. Soc. 1980, 102, 2952-2962.
98. 3) and the cyclooctene analog. Both structures show coordination of the olefin and alkyne orthogonal to the square plane. Intriguingly, both complexes show unsymmetrical coordination of the two π-components, with the α atoms having shorter Rh-C distances than the β atoms, even with a ligand as sterically undemanding as acac; see: (a) Barlow, J. H.; Clark, G. R.; Curl, M. G.; Howden, M. E.; Kemmitt, R. D. W.; Russell, D. R. J. Organomet. Chem. 1978, 144, C47-C51.
99. (b) Barlow, J. H.; Curl, M. G.; Russell, D. R.; Clark, G. R. J. Organomet. Chem. 1982, 235, 231-241.
100. B (or the corresponding transition states). For a review on computational approaches to studying olefin insertion into metal hydrides, see: Niu, S.; Hall, M. B. Chem. Rev. 2000, 100, 363-405, and references therein.