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Timestamp: 2019-04-20 00:45:54+00:00

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Physical Data: mp 57-58 °C.
Solubility: benzene, THF, CH2Cl2, MeCN, DMF.
Form Supplied in: white (colorless) crystalline solid.
Handling, Storage, and Precautions: the solid is irritating to eyes, mucus membranes, and respiratory tract, and physical contact should be avoided. Combustion produces toxic byproducts including nitrogen oxides. Cold storage in air-tight containers is recommended. Use in a fume hood.
Related Reactions of 2-Pyridinethiol Esters.
2-Pyridinethiol esters are readily reduced with Sodium Borohydride in the presence of isopropanol.25 Activation of 2-pyridinethiol esters with Iodomethane allows for mild trapping with alcohols or benzenethiol, yielding esters or thiolesters.26 In these cases the use of iodomethane avoids the need for thiophilic silver or mercury salts and allows for transthiolesterification.
Treatment of glycoside (3) with 2,2�-dipyridyl disulfide and Tri-n-butylphosphine in CH2Cl2 rapidly yields thiopyridyl derivative (4) as a mixture of anomers. Activation of (4) with iodomethane, followed by treatment with glycoside acceptor (5), affords the disaccharide fragment of avermectin (6),27 exclusively a-linked in 78% yield (eq 4).28 Although other methods are available, this protocol offers advantages in practicality and stereoselectivity.
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2. (a) NaOH/KI3: Marckwald, W.; Klemm, W.; Trabert, H. CB 1900, 33, 1556. (b) Nickel peroxide: Nakagawa, K.; Shiba, S.; Horikawa, M.; Sato, K.; Nakamura, H.; Harada, N.; Harada, F. SC 1980, 10, 305. (c) I2: McAllan, D. T.; Cullum, T. V.; Dean, R. A.; Fidler, F. A. JACS 1951, 73, 3627. (d) Zn(BiO3)2: Firouzabadi, H.; Mohammadpour-Baltork, I. BCJ 1992, 65, 1131. (e) (NH4)2Ce(NO3)6 (CAN): Dhar, D. N.; Bag, A. K. IJC(B) 1984, 23B, 974. (f) Bromodimethylsulfonium bromide: Olah, G. A.; Arvanaghi, M.; Vankar, Y. D. S 1979, 721. (g) NaBO3: McKillop, A.; Koyunçu, D. TL 1990, 31, 5007. (h) Diethyl bromomalonate: Kato, E.; Oya, M.; Iso, T.; Iwao, J.-I. CPB 1986, 34, 486. (i) FeCl3-Bu3SnOMe: Sato, T.; Otera, J.; Nozaki, H. TL 1990, 31, 3591.
3. Thalmann, A.; Oertle, K.; Gerlach, H. OSC 1990, 7, 470.
4. Reviews: (a) Nicolaou, K. C. T 1977, 33, 683. (b) Back, T. G. T 1977, 33, 3041. (c) Ogliaruso, M. A.; Wolfe, J. A. In Synthesis of Lactones and Lactams; Patai, S.; Rappaport, Z.; Eds.; Wiley: New York, 1993.
5. Mukaiyama, T. SC 1972, 2, 243.
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9. Corey, E. J.; Nicolaou, K. C.; Melvin, L. S. JACS 1975, 97, 654.
10. Corey, E. J.; Ulrich, P.; Fitzpatrick, J. M. JACS 1976, 98, 222.
11. Corey, E. J.; Nicolaou, K. C.; Toru, T. JACS 1975, 97, 2287.
12. Corey, E. J.; Bhattacharyya, S. TL 1977, 3919.
13. Bundy, G. L.; Peterson, D. C.; Cornette, J. C.; Miller, W. L.; Spilman, C. H.; Wilks, J. W. JMC 1983, 26, 1089.
14. Corey, E. J.; Brunelle, D. J. TL 1976, 3409.
15. (a) Karim, M. R.; Sampson, P. JOC 1990, 55, 598. (b) Justus, K.; Steglich, W. TL 1991, 32, 5781.
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19. Reviews: (a) Klausner, Y. S.; Bodanszky, M. S 1972, 453. (b) Mukaiyama, T. AG(E) 1976, 15, 94.
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22. For other recent methods for the synthesis of 2-acylpyrroles, see: (a) Review: Patterson, J. M. S 1976, 281. (b) Kozikowski, A. P.; Ames, A. JACS 1980, 102, 860. (c) Martinez, G. R.; Grieco, P. A.; Srinivasan, C. V. JOC 1981, 46, 3760. (d) Edwards, M. P.; Ley, S. V.; Lister, S. G.; Palmer, B. D. CC 1983, 630.
23. Nicolaou, K. C.; Claremon, D. A.; Papahatjis, D. P. TL 1981, 22, 4647.
24. Nakahara, Y.; Fujita, A.; Ogawa, T. ABC 1985, 49, 1491.
25. Nicolaou, K. C.; Maligres, P.; Suzuki, T.; Wendeborn, S. V.; Dai, W.-M.; Chadha, R. K. JACS 1992, 114, 8890.
26. Ravi, D.; Mereyala, H. B. TL 1989, 30, 6089.
27. Springer, J. P.; Arison, B. H.; Hirshfield, J. M.; Hoogsteen, K. JACS 1981, 103, 4221.
28. (a) Mereyala, H. B.; Kulkarni, V. R.; Ravi, D.; Sharma, G. V. M.; Rao, B. V.; Reddy, G. B. T 1992, 48, 545. (b) Ravi, D.; Kulkarni, V. R.; Mereyala, H. B. TL 1989, 30, 4287. (c) for mechanistic details see: Mereyala, H. B.; Reddy, G. V. T 1991, 47, 6435.
29. Williams, R. M.; Stewart, A. O. TL 1983, 24, 2715.
30. Craig, D.; Munasinghe, V. R. N. TL 1992, 33, 663.
31. Williams, R. M.; Dung, J.-S.; Josey, J.; Armstrong, R. W.; Meyers, H. JACS 1983, 105, 3214.
32. Nagao, Y.; Seno, K.; Fujita, E. TL 1979, 4403.
33. Nagao, Y.; Takao, S.; Miyasaka, T.; Fujita, E. CC 1981, 286.
34. Dubs, P.; Stüssi, R. HCA 1978, 61, 998.
35. (a) Nakagawa, I.; Hata. T. TL 1975, 1409. (b) Nakagawa, I.; Aki, K.; Hata, T. JCS(P1) 1983, 1315.
36. Kanavorioti, A.; Lu, J.; Rosenbach, M. T.; Hurley, T. B. TL 1991, 32, 6065.
37. Mukaiyama, T.; Hashimoto, M. BCJ 1971, 44, 196.
38. Hata, T.; Sekine, M. TL 1974, 3943.
39. Ebertino, F. H.; Degenhart, C. R.; Jamieson, L. A.; Burdsall, D. C. H 1990, 30, 855.
40. Hirota, K.; Tomishi, T.; Maki, Y. H 1987, 26, 3089.
41. Atkinson, J. G.; Hanel, P.; Girard, Y. S 1988, 480.
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