A remarkable ene-like reaction: Development and synthetic applications

Tetrahedron

Volumn 53, Issue 48, 1997, Pages 16299-16312

  Ciufolini, Marco A ^a   Deaton, Melissa V ^a   Zhu, Shuren ^a   Chen, Mingying ^a  

^a RICE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

2 METHOXYPROPENE; 4 FORMYL 6,9 DIHYDROXY 14 OXA 1,11 DIAZATETRACYCLO[7.4.1.0 2,7 0 10,12]TETRADECA 2,4,6 TRIEN 8 YLMETHYLCARBAMATE; ALDEHYDE; CHLOROVULONE II; CINNAMALDEHYDE; MITOMYCIN C; MITOMYCIN DERIVATIVE; PHYLLANTHOCIN; PROPYLENE; UNCLASSIFIED DRUG; YTTERBIUM;

CATALYSIS; CATALYST; CHEMICAL REACTION; CONFERENCE PAPER; DRUG SYNTHESIS; ENANTIOMER; HYDROLYSIS; PRIORITY JOURNAL; STEREOCHEMISTRY; SYNTHESIS;

EID: 0030778749     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(97)01016-8     Document Type: Conference Paper

References (87)

1. Fellow of the Alfred P. Sloan Foundation, 1994-1996.
2. We stress that the term "ene reaction" is used throughout this discussion only to describe the general structure of the products. No mechanistic inferences should be drawn from this usage.
3. For outstanding reviews see: (a) Snider, B. B., in: Comprehensive Organic Synthesis; Trost, B. M.; Fleming, I., Eds.; Pergamon Press: London, Springer-Verlag: Berlin, Germany, 1986;
4. (b) Santelli, M; Pons, J. M. Lewis Acids and Selectivity in Organic Synthesis; CRC Press: Boca Raton, FL, 1996; ch. 2.
5. Unusually reactive carbonyl compounds may undergo ene reaction in a strictly thermal mode (a) Klimova, E. I.; Antonova, N. D.; Arbuzov, Y. A. J. Org. Chem. USSR (Engl. Transl.) 1969, 5, 1312;
6. (b) Snider, B. B.; van Straten, J. W. J. Org. Chem. 1979, 44, 3567.
7. A number of intramolecular ene reactions may be carried out in truly catalytic mode: (a) Ziegler, F. E.; Sobolov, S. B. J. Am. Chem. Soc. 1990, 112, 2749 (lanthanide catalysis);
8. (b) Gu, J. H.; Terada, M.; Mikami, K.; Nakai, T. Tetrahedron Lett. 1992, 33, 1465;
9. (c) Kobayashi, S.; Hachiya, I. Tetrahedron Lett. 1992, 33, 1625,
10. (d) Mikami, K.; Terada, M.; Nakai, T. J. Org. Chem. 1991, 56, 5456. Recent example of intramolecural ene reaction (requires stoichiometric promoter): Snider, B. B.; Vo, N. H.; O'Neil S. V.; Foxman, B. M. J. Am. Chem. Soc. 1996, 118, 7644.
11. (d) Mikami, K.; Terada, M.; Nakai, T. J. Org. Chem. 1991, 56, 5456. Recent example of intramolecural ene reaction (requires stoichiometric promoter): Snider, B. B.; Vo, N. H.; O'Neil S. V.; Foxman, B. M. J. Am. Chem. Soc. 1996, 118, 7644.
12. (a) Snider, B. B.; Phillips, G. B. J. Am. Chem. Soc. 1982, 104, 1113;
13. (b) Snider, B. B.; Rodini, D. J. Tetrahedron Lett. 1980, 21, 1815;
14. (c) Snider, B. B.; Rodini, D. J.; Kirk, T. C.; Cordova, R. J. Am. Chem. Soc. 1982, 104, 555.
15. (a) Reese, C. B.; Saffhill, R.; Sulston, J. E. J. Am. Chem. Soc. 1967, 89, 3366;
16. (b) Effenberger, F. Angew. Chem., Intl. Ed. Engl. 1969, 8, 295.
17. (c) Isler, O.; Schudel, P. Adv. Org. Chem. 1963, 14, 117. Exception:
18. (d) Kitizawa, E.; Imamura, T.; Saigo, K.; Mukaiyama, T. Chem. Lett. 1975, 569.
19. Mukaiyama, T. Org. React. 1982, 28, 203.
20. Mikami, K.; Matsukawa, S. J. Am. Chem. Soc. 1993, 115, 7039.
21. Shoda, H.; Nakamura, T.; Tanino, K.; Kuwajima, I. Tetrahedron Lett. 1993, 34, 6281.
22. (a) Tanino, K.; Nakamura, T.; Kuwajima, I. Tetrahedron Lett. 1990, 31, 2165;
23. (b) Masuya, K.; Tanino, K.; Kuwajima, I. Tetrahedron Lett. 1994, 35, 7965;
24. (c) Nakamura, T.; Tanino, K.; Kuwajima, I. Tetrahedron Lett. 1993, 34, 477;
25. (d) Tanino, K.; Shoda, H.; Nakamura, T.; Kuwajima, I. Tetrahedron Lett. 1992, 33, 1337.
26. Truly catalytic aldol reactions proper are known, though in their current form they have limited scope. (a) Hayashi, T.; Uozumi, Y.; Yamazaki, A. Tetrahedron Lett. 1991, 32, 2799;
27. (b) Ito, Y.; Sawamura, M.; Hayashi, T. J. Am. Chem. Soc. 1986, 108, 6405.
28. As defined operationally by Bertz, S. J. Am. Chem. Soc. 1981, 103, 3599.
29. Deaton, M. V. Dissertation, Rice University, 1995.
30. Deaton, M. V.; Ciufolini, M. A. Tetrahedron Lett. 1993, 34, 2409.
31. Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc. 1994, 116, 1561.
32. 6 for NMR work. This sensitivity also causes the TLC traces of spectroscopically pure ene products to display several spots, corresponding to substances arising through various modes of acid-promoted decomposition.
33. Cf. Danishefsky, S.; DeNinno, M. P. Tetrahedron Lett. 1985, 26, 823.
34. Still, W. C.; Schneider, J. A. J. Org. Chem. 1980, 45, 3375.
35. Cf.Hart, F. A., in: Comprehensive Coordination Chemistry; Wilkinson, G., Ed.; Pergamon Press: Oxford, UK, 1987; vol. 3, ch. 39. See esp. pp. 1068 ff.
36. Materials such as ethyl vinyl ether or 1-ethoxypropene, wherein this condition is not satisfied, do not undergo the reaction, and the substrate aldehyde is recovered unchanged.
37. Cf. Evans, D. A.; Nelson, J. V.; Taber, T. R. Top. Stereochem. 1982, 13, 1.
38. Discussion: Ciufolini, M. A., in: Advances in Heterocyclic Natural Product Synthesis; Pearson, W. H., Ed.; JAI Press: Greenwich, CT, 1996; vol. 3, p. 1 ff.
39. Ciufolini, M. A.; Bishop, M. J. J. Chem. Soc., Chem. Commun. 1993, 1463.
40. Carreira, E.; Lee, W.; Singer, R. A. J. Am. Chem. Soc. 1995, 117, 3649. See also Prof. Carreira's paper in this issue.
41. We thank Prof. Carreira for stimulating discussion.
42. E.g. antitumor agents (jatrophone: Kupchan, S. M.; Siegel, C. W.; Matz, M. J.; Gilmore, C. J.; Bryan, R. F. J. Am. Chem. Soc. 1976, 98, 2295; eremantholide: Le Quesne, P. W.; Levery, S. B.; Menachery, M. D.; Brennan, T. F.; Raffauf, R. F. J. Chem. Soc., Perkin Trans. 1, 1978, 1572); antiparasitic agents (avermectins and ivermectins: Albers-Schönberg, G.; Arison, B. H.; Chabala, J. C.; Douglas, A. W.; Eskola, P.; Fisher, M. H.; Lusi, A.; Mrozik, H.; Smith, J. L.; Tolman, R. L. J. Am. Chem. Soc. 1981, 103, 4216), etc.
43. E.g. antitumor agents (jatrophone: Kupchan, S. M.; Siegel, C. W.; Matz, M. J.; Gilmore, C. J.; Bryan, R. F. J. Am. Chem. Soc. 1976, 98, 2295; eremantholide: Le Quesne, P. W.; Levery, S. B.; Menachery, M. D.; Brennan, T. F.; Raffauf, R. F. J. Chem. Soc., Perkin Trans. 1, 1978, 1572); antiparasitic agents (avermectins and ivermectins: Albers-Schönberg, G.; Arison, B. H.; Chabala, J. C.; Douglas, A. W.; Eskola, P.; Fisher, M. H.; Lusi, A.; Mrozik, H.; Smith, J. L.; Tolman, R. L. J. Am. Chem. Soc. 1981, 103, 4216), etc.
44. E.g. antitumor agents (jatrophone: Kupchan, S. M.; Siegel, C. W.; Matz, M. J.; Gilmore, C. J.; Bryan, R. F. J. Am. Chem. Soc. 1976, 98, 2295; eremantholide: Le Quesne, P. W.; Levery, S. B.; Menachery, M. D.; Brennan, T. F.; Raffauf, R. F. J. Chem. Soc., Perkin Trans. 1, 1978, 1572); antiparasitic agents (avermectins and ivermectins: Albers-Schönberg, G.; Arison, B. H.; Chabala, J. C.; Douglas, A. W.; Eskola, P.; Fisher, M. H.; Lusi, A.; Mrozik, H.; Smith, J. L.; Tolman, R. L. J. Am. Chem. Soc. 1981, 103, 4216), etc.
45. For the synthesis of specific 3-furanone derivatives see: (a) Sher, F.; Isidor, J. L.; Taneja, H. R.; Carlson, R. M. Tetrahedron Lett. 1973, 577;
46. (b) Reid, W.; Marhold, A. Chem. Ber. 1974, 107, 1714;
47. (c) Carlson, R. M.; Jones, R. W.; Hatcher, A. S. Tetrahedron Lett. 1975, 1714;
48. (d) Gupta, P. K.; Jones, J. G.; Caspi, E. J. Org. Chem. 1975, 40, 1420.
49. Smith, A. B., III; Levenberg, P. A.; Jerris, P. J.; Scarborough, R. M.; Wovkulich, P. M. J. Am. Chem. Soc. 1981, 103, 1501.
50. The stereochemistry of these materials was determined by NOEDS.
51. Huisgens, R. Angew. Chem., Intl. Ed. Engl. 1963, 2, 566.
52. Review: (a) Kishi, Y. J. Nat. Prod. 1979, 42, 549.
53. (b) Fukuyama, T.; Yang, L. J. Am. Chem. Soc. 1987, 109, 7881;
54. (c) Schkeryantz, J. M; Danishefsky, S. J. J. Am. Chem. Soc. 1995, 117, 4722.
55. Ref. 32a as well as: Fukuyama, T.; Xu, L. J. Am. Chem. Soc. 1992, 114, 383.
56. E.g.: (a) Martin, S. F.; Wagman, A. S. Tetrahedron Lett. 1995, 36, 1169;
57. (b) Martin, S. F.; Chen, H. J.; Courtney, A. K.; Liao, Y. S.; Patzel, M.; Ramser, M. N.; Wagman, A. S. Tetrahedron 1996, 52, 7251.
58. Ciufolini, M. A.; Chen, M.; Lovett, D. P.; Deaton, M. V. Tetrahedron Lett. 1997, 38, 4355.
59. Triazolines are often unstable and may spontaneously form aziridines: cf. Morimoto, Y.; Matsuda, F.; Shirahama, H. Tetrahedron Lett. 1990, 31, 6031. It is likely that this is caused by ambient light:
60. Recent reviews covering isolation, bioactivity and synthetic work in this area: (a) Honda, A.; Mori, Y.; Iguchi, K.; Yamada, Y. Molec. Pharm. 1987, 32, 530;
61. (b) Miftakov, M. C.; Adler, M. E.; Akbutnya, F. A.; Tosltikov, G. A. Usp. Khim. 1994, 63, 543;
62. (c) Zhu, J.; Yang, J.-Y.; Klunder, J. H.; Liu, Z.-Y.; Zwanenburg, B. Tetrahedron 1995, 51, 5847.
63. (a) Tsang, R.; Dickson, J. K., Jr.; Pak, H.; Walton, R.; Fraser Reid, B. J. Am. Chem. Soc. 1987, 109, 3484;
64. (b) Walton, R.; Fraser-Reid, B. J. Am. Chem. Soc. 1991, 113, 5791.
65. The stereochemistry of this material was unequivocally established through desilylation and acetonide formation from the intermediate diol.
66. Isolation: Kupchan, S. M.; LaVoie, E. J.; Branfman, A. R.; Fei, B. Y.; Bright, W. M.; Bryan, R. F. J. Am. Chem. Soc. 1977, 99, 3199.
67. (a) McGuirk, P. R.; Collum, D. B. J. Am. Chem. Soc. 1982, 104, 4496;
68. (b) Williams, D. R.; Sit, S. Y. J. Am. Chem. Soc. 1984, 106, 2949;
69. (c) Burke, S. D.; Cobb, J. E. Tetrahedron Lett. 1986, 27, 4237;
70. (d) Burke, S. D.; Cobb, J. E.; Takeuchi, K. J. Org. Chem. 1985, 50, 3420;
71. (e) Smith, A. B., III; Fukui, M. J. Am. Chem. Soc. 1987, 709, 1269;
72. (f) Smith, A. B., III; Fukui, M.; Vaccaro, H. A.; Empfield, J. R. J. Am. Chem. Soc. 1991, 113, 2071;
73. (g) Smith, A. B., III; Fukui, M. J. Am. Chem. Soc. 1987, 109, 1272;
74. (h) Smith, A. B., III; Rivero, R. A.; Hale, K. J.; Vaccaro, H. A. J. Am. Chem. Soc. 1991, 113, 2092;
75. (i) Martin, S. F.; Dappen, M. S.; Dupre, B.; Murphy, C. J. J. Org. Chem. 1987, 52, 3706;
76. (j) Martin, S. F.; Dappen, M. S.; Dupre, B.; Murphy, C. J.; Colapret, J. A. J. Org. Chem. 1989, 54, 2209;
77. (k) Trost, B. M.; Edstrom, E. D. Angew. Chem., Int. Ed. Engl. 1990, 29, 520;
78. (l) Trost, B. M.; Kondo, Y. Tetrahedron Lett. 1991, 32, 1613. Synthetic Studies:
79. (m) Linderman, R. J.; Viviani, F. G.; Kwochka, W. R. Tetrahedron Lett. 1992, 33, 3571;
80. (n) Tenaglia, A.; Kammerer, F. Synlett 1996, 576.
81. Obtained by allylation of butyrolactone (LDA, THF, -78°C, 98%) followed by ozonolysis (97%).
82. The alkylation step (cf. 80 → 81) resulted in cyclopropane formation when an expressed ester was present (selective reaction of the ester enolate). Also, an expressed ketone on the spiropyran unit was not tolerated during this reaction, requiring reduction of 78 to 79. Fortunately, no protection of 79 was necessary. Details will be presented in a separate paper.
83. From the acetylene and BuLi in THF at -78°C.
84. Prepared from commercial 2-methyl-l,3-propanediol: (i) TBS-Cl, DMF, imidazole, 57% (chrom., mono-TBS ether formation); (ii) PCC, 66%; (iii) Corey-Fuchs reaction (63%).
85. Carlsen, P. H. J.; Katsuki, T.; Martin, V. S.; Sharpless, K. B. J. Org. Chem. 1981, 46, 3936.
86. 2CO. MCPBA was purified as detailed below and NBS was recrystallized from water. All other reagents and solvents were used as received.
87. 2 and any insoluble matter was filtered off. Concentration afforded pure, dry MCPBA.