New approaches to olefin cross-metathesis

Journal of the American Chemical Society

Volumn 122, Issue 1, 2000, Pages 58-71

  Blackwell, Helen E ^a   O'Leary, Daniel J ^b   Chatterjee, Arnab K ^a   Washenfelder, Rebecca A ^b   Bussmann, D Andrew ^b   Grubbs, Robert H ^a  

^a California Institute of Technology   (United States)

^b POMONA COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE;

ARTICLE; CHEMICAL REACTION; DIMERIZATION; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; SYNTHESIS;

EID: 0034639441     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja993063u     Document Type: Article

References (128)

1. For preliminary accounts of this work, see: (a) O'Leary, D. J.; Blackwell, H. E.; Washenfelder, R. A.; Grubbs, R. H. Tetrahedron Lett. 1998, 39, 7427-7430. (b) O'Leary, D. J.; Blackwell, H. E.; Washenfelder, R. A.; Miura, K.; Grubbs, R. H. Tetrahedron Lett. 1999, 40, 1091-1094. (c) Blackwell, H. E. Ph.D. Thesis, California Institute of Technology, 1999.
2. For preliminary accounts of this work, see: (a) O'Leary, D. J.; Blackwell, H. E.; Washenfelder, R. A.; Grubbs, R. H. Tetrahedron Lett. 1998, 39, 7427-7430. (b) O'Leary, D. J.; Blackwell, H. E.; Washenfelder, R. A.; Miura, K.; Grubbs, R. H. Tetrahedron Lett. 1999, 40, 1091-1094. (c) Blackwell, H. E. Ph.D. Thesis, California Institute of Technology, 1999.
3. For preliminary accounts of this work, see: (a) O'Leary, D. J.; Blackwell, H. E.; Washenfelder, R. A.; Grubbs, R. H. Tetrahedron Lett. 1998, 39, 7427-7430. (b) O'Leary, D. J.; Blackwell, H. E.; Washenfelder, R. A.; Miura, K.; Grubbs, R. H. Tetrahedron Lett. 1999, 40, 1091-1094. (c) Blackwell, H. E. Ph.D. Thesis, California Institute of Technology, 1999.
4. For general olefin metathesis references, see: (a) Ivin, K. J.; Mol, J. C. Olefin Metathesis and Metathesis Polymerization, 2nd ed.; Academic: San Diego, 1997. (b) Grubbs, R. H.; Pine, S. H. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon: New York: 1991; Vol. 5, Chapter 9.3.
5. For general olefin metathesis references, see: (a) Ivin, K. J.; Mol, J. C. Olefin Metathesis and Metathesis Polymerization, 2nd ed.; Academic: San Diego, 1997. (b) Grubbs, R. H.; Pine, S. H. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon: New York: 1991; Vol. 5, Chapter 9.3.
6. For details of the present accepted mechanism of olefin metathesis involving formation of a metallocydobutane intermediate, see: Herrison, J. L.; Chauvin, Y. Makromol. Chem. 1971, 141, 161-176.
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10. For recent reviews of RCM in organic synthesis, see: (a) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (b) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (c) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1833-1836. (d) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-552.
11. For recent reviews of RCM in organic synthesis, see: (a) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (b) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (c) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1833-1836. (d) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-552.
12. For recent reviews of RCM in organic synthesis, see: (a) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450. (b) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (c) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1833-1836. (d) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-552.
13. 3 = tricyclohexylphosphine. For the preparation and characterization of catalyst 1, see: (a) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041. (b) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110. (c) Belderrain, T. R.; Grubbs, R. H. Organometallics 1997, 16, 4001-4003.
14. 3 = tricyclohexylphosphine. For the preparation and characterization of catalyst 1, see: (a) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041. (b) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110. (c) Belderrain, T. R.; Grubbs, R. H. Organometallics 1997, 16, 4001-4003.
15. 3 = tricyclohexylphosphine. For the preparation and characterization of catalyst 1, see: (a) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041. (b) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110. (c) Belderrain, T. R.; Grubbs, R. H. Organometallics 1997, 16, 4001-4003.
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19. Issues of poor selectivity plagued early CM efforts employing "classical" catalysts. For a recent review of CM using "classical" catalysts, see: Finkel'shtein, E. S.; Bykov, V. I.; Portnykh, E. B. J. Mol. Catal. 1992, 76, 33-52.
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27. Crowe, W. E.; Goldberg, D. R.; Zhang, Z. J. Tetrahedron Lett. 1996, 37, 2117-2120.
28. For the ruthenium-catalyzed CM of functionalized terminal olefins with allyldimethylsilyl-derivatized polystyrene resin, see: Schuster, M.; Lucas, N.; Blechert, S. Chem. Commun. 1997, 823-824.
29. Brümmer, O.; Rückert, A.; Blechert, S. Chem. Eur. J. 1997, 3, 441-446.
30. Highly functionalized silsesquioxanes and spherosilicates have been prepared via the CM of various alkenes with vinyl-substituted silsesquioxane and spherosilicate frameworks employing molybdenum alkylidene 2. The lack of homodimerization of the vinyl-substituted silicon frameworks was attributed to steric bulk. See: Feher, F. J.; Soulivong, D.; Eklund, A. G.; Wyndham, K. D. J. Chem. Soc., Chem. Commun. 1997, 1185-1186.
31. (a) Gibson, S. E.; Gibson, V. C.; Keen, S. P. Chem. Commun. 1997, 1107-1108.
32. (b) Baigini, S. C. G.; Gibson, S. E.; Keen, S. P. J. Chem. Soc., Perkin Trans. 1 1998, 16, 2485-2499.
33. For solution-phase yne-ene metathesis employing alkylidene 1, see: (a) Stragies, R.; Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2518-2520.
34. For solid-phase yne-ene metathesis employing catalyst 1, see: (b) Schürer, S. C.; Blechert, S. Synlett 1998, 166-168. (c) Schuster, M.; Blechert, S. Tetrahedron Lett. 1998, 39, 2295-2298.
35. For solid-phase yne-ene metathesis employing catalyst 1, see: (b) Schürer, S. C.; Blechert, S. Synlett 1998, 166-168. (c) Schuster, M.; Blechert, S. Tetrahedron Lett. 1998, 39, 2295-2298.
36. For recent ROM references, see: (a) Randall, M. L.; Tallarico, J. A.; Snapper, M. L. J. Am. Chem. Soc. 1995, 117, 9610-9611. (b) Schneider, M. F.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 411-412. (c) Schneider, M. F.; Lucas, N.; Velder, J.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 257-259. (d) Snapper, M. L.; Tallarico, J. A.; Randall, M. L. J. Am. Chem. Soc, 1997, 119, 1478-1479. (e) Tallarico, J. A.; Bonitatebus, P. J.; Snapper, M. L. J. Am. Chem. Soc. 1997, 119, 7157-7158. (f) Tallarico, J. A.; Randall, M. L.; Snapper, M. L. Tetrahedron 1997, 53, 16511-16520. (g) Cuny, G. D.; Cao, J.; Hauske, J. R. Tetrahedron Lett. 1997, 38, 5237-5240. (h) Cao, J.; Cuny, G. D.; Hauske, J. R. Mol. Divers. 1998, 3, 173-179.
37. For recent ROM references, see: (a) Randall, M. L.; Tallarico, J. A.; Snapper, M. L. J. Am. Chem. Soc. 1995, 117, 9610-9611. (b) Schneider, M. F.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 411-412. (c) Schneider, M. F.; Lucas, N.; Velder, J.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 257-259. (d) Snapper, M. L.; Tallarico, J. A.; Randall, M. L. J. Am. Chem. Soc, 1997, 119, 1478-1479. (e) Tallarico, J. A.; Bonitatebus, P. J.; Snapper, M. L. J. Am. Chem. Soc. 1997, 119, 7157-7158. (f) Tallarico, J. A.; Randall, M. L.; Snapper, M. L. Tetrahedron 1997, 53, 16511-16520. (g) Cuny, G. D.; Cao, J.; Hauske, J. R. Tetrahedron Lett. 1997, 38, 5237-5240. (h) Cao, J.; Cuny, G. D.; Hauske, J. R. Mol. Divers. 1998, 3, 173-179.
38. For recent ROM references, see: (a) Randall, M. L.; Tallarico, J. A.; Snapper, M. L. J. Am. Chem. Soc. 1995, 117, 9610-9611. (b) Schneider, M. F.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 411-412. (c) Schneider, M. F.; Lucas, N.; Velder, J.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 257-259. (d) Snapper, M. L.; Tallarico, J. A.; Randall, M. L. J. Am. Chem. Soc, 1997, 119, 1478-1479. (e) Tallarico, J. A.; Bonitatebus, P. J.; Snapper, M. L. J. Am. Chem. Soc. 1997, 119, 7157-7158. (f) Tallarico, J. A.; Randall, M. L.; Snapper, M. L. Tetrahedron 1997, 53, 16511-16520. (g) Cuny, G. D.; Cao, J.; Hauske, J. R. Tetrahedron Lett. 1997, 38, 5237-5240. (h) Cao, J.; Cuny, G. D.; Hauske, J. R. Mol. Divers. 1998, 3, 173-179.
39. For recent ROM references, see: (a) Randall, M. L.; Tallarico, J. A.; Snapper, M. L. J. Am. Chem. Soc. 1995, 117, 9610-9611. (b) Schneider, M. F.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 411-412. (c) Schneider, M. F.; Lucas, N.; Velder, J.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 257-259. (d) Snapper, M. L.; Tallarico, J. A.; Randall, M. L. J. Am. Chem. Soc, 1997, 119, 1478-1479. (e) Tallarico, J. A.; Bonitatebus, P. J.; Snapper, M. L. J. Am. Chem. Soc. 1997, 119, 7157-7158. (f) Tallarico, J. A.; Randall, M. L.; Snapper, M. L. Tetrahedron 1997, 53, 16511-16520. (g) Cuny, G. D.; Cao, J.; Hauske, J. R. Tetrahedron Lett. 1997, 38, 5237-5240. (h) Cao, J.; Cuny, G. D.; Hauske, J. R. Mol. Divers. 1998, 3, 173-179.
40. For recent ROM references, see: (a) Randall, M. L.; Tallarico, J. A.; Snapper, M. L. J. Am. Chem. Soc. 1995, 117, 9610-9611. (b) Schneider, M. F.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 411-412. (c) Schneider, M. F.; Lucas, N.; Velder, J.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 257-259. (d) Snapper, M. L.; Tallarico, J. A.; Randall, M. L. J. Am. Chem. Soc, 1997, 119, 1478-1479. (e) Tallarico, J. A.; Bonitatebus, P. J.; Snapper, M. L. J. Am. Chem. Soc. 1997, 119, 7157-7158. (f) Tallarico, J. A.; Randall, M. L.; Snapper, M. L. Tetrahedron 1997, 53, 16511-16520. (g) Cuny, G. D.; Cao, J.; Hauske, J. R. Tetrahedron Lett. 1997, 38, 5237-5240. (h) Cao, J.; Cuny, G. D.; Hauske, J. R. Mol. Divers. 1998, 3, 173-179.
41. For recent ROM references, see: (a) Randall, M. L.; Tallarico, J. A.; Snapper, M. L. J. Am. Chem. Soc. 1995, 117, 9610-9611. (b) Schneider, M. F.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 411-412. (c) Schneider, M. F.; Lucas, N.; Velder, J.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 257-259. (d) Snapper, M. L.; Tallarico, J. A.; Randall, M. L. J. Am. Chem. Soc, 1997, 119, 1478-1479. (e) Tallarico, J. A.; Bonitatebus, P. J.; Snapper, M. L. J. Am. Chem. Soc. 1997, 119, 7157-7158. (f) Tallarico, J. A.; Randall, M. L.; Snapper, M. L. Tetrahedron 1997, 53, 16511-16520. (g) Cuny, G. D.; Cao, J.; Hauske, J. R. Tetrahedron Lett. 1997, 38, 5237-5240. (h) Cao, J.; Cuny, G. D.; Hauske, J. R. Mol. Divers. 1998, 3, 173-179.
42. For recent ROM references, see: (a) Randall, M. L.; Tallarico, J. A.; Snapper, M. L. J. Am. Chem. Soc. 1995, 117, 9610-9611. (b) Schneider, M. F.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 411-412. (c) Schneider, M. F.; Lucas, N.; Velder, J.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 257-259. (d) Snapper, M. L.; Tallarico, J. A.; Randall, M. L. J. Am. Chem. Soc, 1997, 119, 1478-1479. (e) Tallarico, J. A.; Bonitatebus, P. J.; Snapper, M. L. J. Am. Chem. Soc. 1997, 119, 7157-7158. (f) Tallarico, J. A.; Randall, M. L.; Snapper, M. L. Tetrahedron 1997, 53, 16511-16520. (g) Cuny, G. D.; Cao, J.; Hauske, J. R. Tetrahedron Lett. 1997, 38, 5237-5240. (h) Cao, J.; Cuny, G. D.; Hauske, J. R. Mol. Divers. 1998, 3, 173-179.
43. For recent ROM references, see: (a) Randall, M. L.; Tallarico, J. A.; Snapper, M. L. J. Am. Chem. Soc. 1995, 117, 9610-9611. (b) Schneider, M. F.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 411-412. (c) Schneider, M. F.; Lucas, N.; Velder, J.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 257-259. (d) Snapper, M. L.; Tallarico, J. A.; Randall, M. L. J. Am. Chem. Soc, 1997, 119, 1478-1479. (e) Tallarico, J. A.; Bonitatebus, P. J.; Snapper, M. L. J. Am. Chem. Soc. 1997, 119, 7157-7158. (f) Tallarico, J. A.; Randall, M. L.; Snapper, M. L. Tetrahedron 1997, 53, 16511-16520. (g) Cuny, G. D.; Cao, J.; Hauske, J. R. Tetrahedron Lett. 1997, 38, 5237-5240. (h) Cao, J.; Cuny, G. D.; Hauske, J. R. Mol. Divers. 1998, 3, 173-179.
44. For a novel variant of ROM including a tandem RCM reaction, see: Stragies, R.; Blechert, S. Synlett 1998, 169-170.
45. (a) Boger, D. L.; Chai, W.; Ozer, R. S.; Anderson, C.-M. Biorg. Med. Chem. Lett. 1997, 7, 463-468.
46. (b) Boger, D. L.; Chai, W. Tetrahedron 1998, 54, 3955-3970.
47. (c) Boger, D. L.; Chai, W.; Jin, Q. J. Am. Chem. Soc. 1998, 120, 7220-7225.
48. (d) Giger, T.; Wigger, M.; Audétat, S.; Benner, S. A. Synlett 1998, 688-691.
49. (e) Brandli, C.; Ward, T. R. Helv. Chim. Acta 1998, 81, 1616-1621.
50. For a recent report from these laboratories, see: Hillmyer, M. A.; Nguyen, S. T.; Grubbs, R. H. Macromolecules 1997, 30, 718-721 and references therein.
51. Prepared according to a general literature procedure: Schlessinger, R. H.; Lopes, A. J. Org. Chem. 1981, 46, 5252-5253.
52. 13C NMR, and HRMS) can be found in the Supporting Information.
53. This is the exact opposite effect that Blechen et al. observed in the ROM of cyclic olefins with monosubstituted olefins versus disubstituted olefins. A large excess (up to 10-fold) of the less reactive disubstituted olefin was required to suppress the ROMP of the strained cyclic olefin substrates, while only 1 equiv of the corresponding monosubstituted olefin was required to effect analogous yields. See ref 18b.
54. Ullman, M.; Grubbs, R. H. Organometallics 1998, 17, 2484-2489.
55. Prepared according to a standard literature procedure: Lardon, A.; Reichstein, T. Helv. Chim. Acta 1954, 37, 443-450.
56. Prepared using a general method: Alexakis, A.; Gardette, M.; Colin, S. Tetrahedron Lett. 1988, 29, 2951-2954.
57. Prepared using a general method: Chaudary, S. K.; Hernandez, O. Tetrahedron Lett. 1979, 2, 95-98.
58. Prepared by a general procedure: Forster, R. C.; Owen, L. N. J. Chem. Soc., Perkin Trans. 1 1978, 822-829.
59. Prepared using a general method: Corey, E. J.; Venkateswarlu, A. J. Am. Chem. Soc. 1972, 94, 6190-6191.
60. Prepared according to a modified literature procedure. See: Zuwen, H.; Nadkarni, D. V.; Sayre, L. M.; Greenaway, F. T. Biochim. Biophys. Acta 1995, 1253, 117-127.
61. This corroborated well with the observation of Blechert et al. that trans-disubstituted internal olefins are reactive substrates for ROM. See ref 18b.
62. Prepared according to a literature procedure: Gassman, P. G.; Bonser, S. M.; Mlinaric-Majerski, K. J. Am. Chem. Soc. 1989, 111, 2652-2662.
63. Prepared via a DCC coupling between trans-β-hydromuconic acid and N,O-dimethylhydroxylamine hydrochloride. See: Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22, 3815-3818.
64. Prepared according to a general literature procedure: Zhdanov, R. I.; Zhenodarova, S. M. Synthesis 1975, 222-245.
65. Nubel, P. O.; Yokelson, H. B.; Lutman, C. A.; Bouslog, W. G.; Behrends, R. T.; Runge, K. D. J. Mol. Catal. A 1997, 115, 43-50.
66. The self-metathesis of terminai olefins employing "classical" olefin metathesis catalysts has been utilized previously in the synthesis of symmetrically disubstituted olefins. The majority of these applications involved the synthesis of structurally simple, aliphatic internal alkenes. See: (a) Marciniec, B.; Gulinski, J. J. Organomet. Chem. 1984, 266, C19-C21. (b) Marciniec, B.; Maciejewski, H.; Gullinski, J.; Rzejak, Z. J. Organomet. Chem. 1989, 362, 273-279. (c) Marciniec, B.; Pietraszuk, C.; Foltynowicz, Z. J. Organomet. Chem. 1994, 474, 83-87.
67. The self-metathesis of terminai olefins employing "classical" olefin metathesis catalysts has been utilized previously in the synthesis of symmetrically disubstituted olefins. The majority of these applications involved the synthesis of structurally simple, aliphatic internal alkenes. See: (a) Marciniec, B.; Gulinski, J. J. Organomet. Chem. 1984, 266, C19-C21. (b) Marciniec, B.; Maciejewski, H.; Gullinski, J.; Rzejak, Z. J. Organomet. Chem. 1989, 362, 273-279. (c) Marciniec, B.; Pietraszuk, C.; Foltynowicz, Z. J. Organomet. Chem. 1994, 474, 83-87.
68. The self-metathesis of terminai olefins employing "classical" olefin metathesis catalysts has been utilized previously in the synthesis of symmetrically disubstituted olefins. The majority of these applications involved the synthesis of structurally simple, aliphatic internal alkenes. See: (a) Marciniec, B.; Gulinski, J. J. Organomet. Chem. 1984, 266, C19-C21. (b) Marciniec, B.; Maciejewski, H.; Gullinski, J.; Rzejak, Z. J. Organomet. Chem. 1989, 362, 273-279. (c) Marciniec, B.; Pietraszuk, C.; Foltynowicz, Z. J. Organomet. Chem. 1994, 474, 83-87.
69. Prepared via a DCC coupling between N-Boc-glycine-OH and 9-decen-1-ol.
70. Moderate trans selectivity has been consistently observed in almost all intermolecular metathesis accounts employing benzylidene 1 to date. This selectivity is consistent with preferential formation of trans-α,β-disubstituted metallocyclobutane intermediates. We made the assumption that the predominant olefin regioisomer for these symmetrical homodimers was trans in our NMR spectroscopic analyses.
71. Allyl benzene (27) has been previously reported by Benner et al. to be an excellent substrate for the synthesis of combinatorial libraries via CM. See ref 20d.
72. The allyl ether was introduced into 1-ferrocene methanol using a standard literature procedure: Corey, E. J.; Suggs, J. W. J. Org. Chem. 1973, 38, 3224.
73. 1H NMR and mp data (30: 91°C, lit. mp 94-94.5°C) with the known E-1,4-bis(pentafluorophenyl)-2-butene: Filler, R.; Choe, E. W. Can. J. Chem. 1975, 53, 1491-1495.
74. (O)-Allyl ethers of L-serine, L-homoserine, and L-tyrosine have been previously employed in the synthesis of peptide macrocycles via RCM. See: (a) Miller, S. J.; Blackwell, H. E.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118, 9606-9614. (b) Blackwell, H. E.; Grubbs, R. H. Angew. Chem., Int. Ed. 1998, 37, 3281-3284.
75. (O)-Allyl ethers of L-serine, L-homoserine, and L-tyrosine have been previously employed in the synthesis of peptide macrocycles via RCM. See: (a) Miller, S. J.; Blackwell, H. E.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118, 9606-9614. (b) Blackwell, H. E.; Grubbs, R. H. Angew. Chem., Int. Ed. 1998, 37, 3281-3284.
76. O'Leary, D. J.; Miller, S. J.; Grubbs, R. H. Tetrahedron Lett. 1998, 39, 1689-1690.
77. For the synthesis of C-allylglucoside 43, see: Lewis, M. D.; Cha, J. K.; Kishi, Y. J. Am. Chem. Soc. 1982, 104, 4976-4978.
78. Terminal olefin derived sugars and amino acids have previously been employed in CM with other terminal olefins. See refs 13 and 46b.
79. For recent syntheses of carbon-carbon linked glycosyl amino acids, see: (a) Dondoni, A.; Marra, A.; Massi, A. J. Chem. Soc., Chem Commun. 1998, 1741-1742. (b) Dondoni, A.; Massi, A.; Marra, A. Tetrahedron Lett. 1998, 39, 6601-6604. (c) Hu, Y.-J.; Roy, R. Tetrahedron Lett. 1999, 40, 3305-3308.
80. For recent syntheses of carbon-carbon linked glycosyl amino acids, see: (a) Dondoni, A.; Marra, A.; Massi, A. J. Chem. Soc., Chem Commun. 1998, 1741-1742. (b) Dondoni, A.; Massi, A.; Marra, A. Tetrahedron Lett. 1998, 39, 6601-6604. (c) Hu, Y.-J.; Roy, R. Tetrahedron Lett. 1999, 40, 3305-3308.
81. For recent syntheses of carbon-carbon linked glycosyl amino acids, see: (a) Dondoni, A.; Marra, A.; Massi, A. J. Chem. Soc., Chem Commun. 1998, 1741-1742. (b) Dondoni, A.; Massi, A.; Marra, A. Tetrahedron Lett. 1998, 39, 6601-6604. (c) Hu, Y.-J.; Roy, R. Tetrahedron Lett. 1999, 40, 3305-3308.
82. Racemic allylic-substituted terminal olefins were employed in these CM studies
83. Prepared according to a literature procedure: Hanessian, S.; Lavallee, P. Can. J. Chem. 1975, 53, 2975-2977.
84. The methylidene content was found to diminish when the NMR tubes were periodically purged with argon.
85. Chelation of functionality in the allylic position of the metal alkylidene to the metal center should be disfavored because this would form a strained, four-membered ring.
86. The poorer performance of disubstituted "isolated" olefins in CM reactions could also be due to a slower rate of CM, a rate that becomes competitive with the intrinsic rate of catalyst decomposition. (46) For recent CM and RCM applications in carbohydrate synthesis, see: (a) Feng, J.; Schuster, M.; Blechert, S. Synlett 1997, 129-130. (b) El Sukkari, H.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (c) Fürstner, A.; Müller, T. J. Org. Chem. 1998, 63, 424-425. (d) Calimente, D.; Postema, M. H. D. J. Org. Chem. 1999, 64, 1770-1771. (e) Postema, M. H. D.; Calimente, D. Tetrahedron Lett. 1999, 40, 4755-4759.
87. The poorer performance of disubstituted "isolated" olefins in CM reactions could also be due to a slower rate of CM, a rate that becomes competitive with the intrinsic rate of catalyst decomposition. (46) For recent CM and RCM applications in carbohydrate synthesis, see: (a) Feng, J.; Schuster, M.; Blechert, S. Synlett 1997, 129-130. (b) El Sukkari, H.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (c) Fürstner, A.; Müller, T. J. Org. Chem. 1998, 63, 424-425. (d) Calimente, D.; Postema, M. H. D. J. Org. Chem. 1999, 64, 1770-1771. (e) Postema, M. H. D.; Calimente, D. Tetrahedron Lett. 1999, 40, 4755-4759.
88. The poorer performance of disubstituted "isolated" olefins in CM reactions could also be due to a slower rate of CM, a rate that becomes competitive with the intrinsic rate of catalyst decomposition. (46) For recent CM and RCM applications in carbohydrate synthesis, see: (a) Feng, J.; Schuster, M.; Blechert, S. Synlett 1997, 129-130. (b) El Sukkari, H.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (c) Fürstner, A.; Müller, T. J. Org. Chem. 1998, 63, 424-425. (d) Calimente, D.; Postema, M. H. D. J. Org. Chem. 1999, 64, 1770-1771. (e) Postema, M. H. D.; Calimente, D. Tetrahedron Lett. 1999, 40, 4755-4759.
89. The poorer performance of disubstituted "isolated" olefins in CM reactions could also be due to a slower rate of CM, a rate that becomes competitive with the intrinsic rate of catalyst decomposition. (46) For recent CM and RCM applications in carbohydrate synthesis, see: (a) Feng, J.; Schuster, M.; Blechert, S. Synlett 1997, 129-130. (b) El Sukkari, H.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (c) Fürstner, A.; Müller, T. J. Org. Chem. 1998, 63, 424-425. (d) Calimente, D.; Postema, M. H. D. J. Org. Chem. 1999, 64, 1770-1771. (e) Postema, M. H. D.; Calimente, D. Tetrahedron Lett. 1999, 40, 4755-4759.
90. The poorer performance of disubstituted "isolated" olefins in CM reactions could also be due to a slower rate of CM, a rate that becomes competitive with the intrinsic rate of catalyst decomposition. (46) For recent CM and RCM applications in carbohydrate synthesis, see: (a) Feng, J.; Schuster, M.; Blechert, S. Synlett 1997, 129-130. (b) El Sukkari, H.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (c) Fürstner, A.; Müller, T. J. Org. Chem. 1998, 63, 424-425. (d) Calimente, D.; Postema, M. H. D. J. Org. Chem. 1999, 64, 1770-1771. (e) Postema, M. H. D.; Calimente, D. Tetrahedron Lett. 1999, 40, 4755-4759.
91. For leading references to peptide RCM, see refs 5a and 43.
92. Another role of the disubstituted olefin may be to limit formation of a particular metallacycle that reduces catalytic efficiency because it is either less unreactive or readily decomposes. Because this type of role relates directly to the nature of the olefin substituent, it appears to be more consistent with the unique behavior exhibited by olefins containing proximal polar or sterically bulky groups. Two possibilities for the "unfavored" metallacycle, requiring a monosubstituted olefin for its formation, are as follows: (Matrix Presented)
93. For recent reviews, see: (a) Kelly, S. E. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: New York, 1991; Vol. 1, Chapter 3, pp 755-782. (b) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 863-927.
94. For recent reviews, see: (a) Kelly, S. E. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: New York, 1991; Vol. 1, Chapter 3, pp 755-782. (b) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 863-927.
95. Bestmann, H. J.; Vostrowsky, O.; Paulus, H.; Billman, W.; Stransky, W. Tetrahedron Lett. 1977, 121-124.
96. Daubresse, N.; Francesch, C.; Rolando, C. Tetrahedron 1998, 54, 10761-10770.
97. Meyers, A. I.; Tomioka, K.; Fleming, M. P. J. Org. Chem. 1978, 43, 3788-3789.
98. Wollenberg, R. H.; Albizati, K. F.; Peries, R. J. Am. Chem. Soc. 1977, 99, 7365-7367.
99. Wittig, G.; Reiff, H. Angew. Chem., Int. Ed. Engl. 1968, 80, 8-15.
100. Meyers, A. I.; Nabeya, A.; Adickes, H. W.; Politzer, I. R.; Malone, G. R.; Kovelesky, A. C.; Nolen, R. L.; Portnoy, R. C. J. Org. Chem. 1973, 38, 36-56.
101. For a recent example of an acrolein acetal used in an RCM reaction, see: (a) Crimmins, M. T.; King, B. W. J. Am. Chem. Soc. 1998, 120, 9084-9085.
102. For the recent report of the ROM of cyclopropenone ketal with terminal olefins, see: (b) Michaut, M.; Parrain, J.-L.; Santelli, M. Chem. Commun. 1998, 2567-2568.
103. Allylbenzene has recently been reported to efficiently undergo CM reactions with acrolein, acrolein dimethyl acetal, and acrylonitrile catalyzed by ruthenium benzylidene 1. We have not observed productive CM with olefin 3 and either acrolein or acrylonitrile in our laboratory. See: Blanco, O. M.; Castedo, L. Synlett 1999, 557-558.
104. Gemal, A. L.; Luche, J. L. Tetrahedron Lett. 1981, 4077-4080.
105. Prepared via a literature procedure. See: Gassman, P. G.; Chavan, S. J. Chem. Soc., Chem. Commun. 1989, 837-839.
106. Prepared via a literature procedure. See: Gassman, P. G.; Burns, S. J.; Pfister, K. B. J. Org. Chem. 1993, 58, 1449-1457.
107. Cyclic diacetals of fumaraldehyde have been prepared previously. See: Sokolov, G. P.; Hillers, S. Khim. Geterotsikl. Soedin. 1969, 1, 32-35.
108. For an example of an asymmetric Simmons-Smith reaction using tartrate-cierived α,β-unsaturated acetals, see: Mori, A.; Arai, I.; Yamamoto, H. Tetrahedron 1986, 42, 6447-6458.
109. Tsuzuki, T.; Koyama, M.; Tanabe, K. Bull. Chem. Soc. Jpn. 1967, 40, 1008-1013.
110. 1H NMR of the crude tartrate CM product 80. The yield of lartrate CM product 80 was determined after acid hydrolysis of the acetal to afford aldehyde 69.
111. (a) Fujimura, O.; dela Mata, F. J.; Grubbs, R. H. Organometallics 1996, 15, 1865-1871.
112. (b) Fujimura, O.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118, 2499-2500.
113. (c) Fujimura, O.; Grubbs, R. H. J. Org. Chem. 1998, 63, 824-832.
114. (d) Alexander, J. B.; La, D. S.; Cefalo, D. R.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 4041-4042.
115. (e) La, D. S.; Alexander, J. B.; Cefalo, D. R.; Graf, D. D.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 1998, 120, 9720-9721.
116. For a recent example of the synthesis of cyclic alkenylboronates via RCM employing ruthenium catalyst 1, see: Renaud, J.; Ouellet, S. G. J. Am. Chem. Soc. 1998, 120, 7995-7996.
117. Prepared according to a literature procedure: Hunt, A. R.; Stewart, S. K.; Whiting, A. Tetrahedron Lett. 1993, 34, 3599-3602.
118. Suzuki, A. Pure Appl. Chem. 1986, 58, 629-638.
119. Converting a terminal olefin to a vinylboronic acid or protected variant for the Suzuki coupling reaction often requires a three-step procedure involving (1) oxidative cleavage to the aldehyde, (2) subsequent reaction with dimethyl diazomethylphosphonate to provide the terminal alkyne, and (3) finally, conversion to the vinylboronate by hydroboration. For a recent example, see: Scheldt, K. A.; Tasaka, A.; Bannister, T. D.; Wendt, M. D.; Roush, W. R. Angew. Chem., Int. Ed. 1999, 38, 1652-1655.
120. The natural product FK506 was recently homodimerized employing 1 through its endogenous C(28) allyl group to yield a cell-permeable protein dimerizer, FK1012. See: Diver, S. T.; Schreiber, S. L. J. Am. Chem. Soc. 1997, 119, 5106-5109.
121. For the RCM of alkenyl phosphonates employing 1, see: Hanson, P. R.; Stoianova, D. S. Tetrahedron Lett. 1998, 39, 3939-3942.
122. Preliminary results from these laboratories show that alkenyl ester derivatives of cysteine are active substrates for CM.
123. Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923-2925.
124. The solvent columns are composed of activated alumina (A-2) and supported copper redox catalyst (Q-5 reactant). See: Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organametallics 1996, 15, 1518-1520.
125. For the allylation procedure, see: Sugano, H.; Miyoshi, M. J. Org. Chem. 1976, 41, 2352-2353. For the methyl ester formation, see: Hirai, Y.; Aida, T.; Inoue, S. J. Am. Chem. Soc. 1989, 111, 3062-3063.
126. For the allylation procedure, see: Sugano, H.; Miyoshi, M. J. Org. Chem. 1976, 41, 2352-2353. For the methyl ester formation, see: Hirai, Y.; Aida, T.; Inoue, S. J. Am. Chem. Soc. 1989, 111, 3062-3063.
127. Bodansky, M. Peptide Chemistry: Springer-Verlag: New York, 1988; pp 55-146 and references therein.
128. Prepared according to a general literature procedure: Schlessinger, R. H.; Lopes, A. J. Org. Chem. 1981, 46, 5252-5253.