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Solubility: sol THF, DMSO, 1,4-dioxane, DMF.
Preparative Method: usually generated in situ by the reaction of trimethylsulfoxonium iodide or chloride with strong base in a appropriate solvent without drying or further purification; not commercially available.
Handling, Storage, and Precautions: reactions using this nucleophilic reagent should be carried out under an inert atmosphere; it is more stable than Dimethylsulfonium Methylide and can be stored in solution under N2 at 0 °C for months without appreciable decomposition.
Preparations of sulfur ylides under phase-transfer catalyzed conditions have also been reported. One such system involved the use of CH2Cl2, Tetra-n-butylammonium Iodide (TBAI), NaOH, and trimethylsulfoxonium iodide.12 N-Benzyl-N,N,N-trimethylammonium chloride has also been reported as an efficient catalyst for this reaction.13 An alternative system using trimethylsulfoxonium iodide, cetrimide (cetyltrimethylammonium bromide), aqueous NaOH, and 1,1,1-trichloroethane has also been reported.14 Usually, the phase-transfer catalyzed reactions are performed at elevated temperatures from 50 to 75 °C.
Instead of using strong base in an anhydrous media, epoxides have also been prepared under phase-transfer catalysis conditions with a sulfur ylide.12-14,20,21 Activated Barium Hydroxide was reported to catalyze the oxirane formation in interfacial solid-liquid conditions.22,23 These reactions were performed in MeCN in the presence of Ba(OH)2 with a small amount of H2O.
The condensation of 1-tetralone with dimethylsulfoxonium methylide affords the corresponding oxirane in 75% yield.24,25 However, if this parent ketone possesses an aromatic electron-releasing substituent such as a methoxy group, the resulting spiro-oxirane may not be stable and may readily rearrange to give ring-opened compounds.
Reactions of hydroxybenzopyranones, hydroxyphenylalkanones, and 2-(o-hydroxyphenyl)alkyl ketones with dimethylsulfoxonium methylide provide an efficient route to oxygen heterocycles (eq 10).31-33 The mechanism involves an intramolecular ring opening of the oxirane intermediate.
Several examples of conversion of chiral ketones and aldehydes to epoxides with high diastereomeric purity have been reported.36-38 Stereoselective reaction of the nucleoside 2�-keto-3�,5�-O-(tetraisopropyldisiloxane-1,3-diyl)uridine with dimethylsulfoxonium methylide at 0 °C afforded only one isomer of the product epoxide in 63% yield.39 Reaction of the heterocyclic carbonyl compounds with dimethylsulfoxonium methylide also provided the corresponding oxiranes, such as 1-oxa-6-heterospiro[2,5]octanes, in good yields and isomeric purities.40,41 One example showed that dimethylsulfoxonium methylide reacted chemoselectively with the five-membered ketone ring in the presence of the six-membered carbonyl function to give the monoepoxide in good yield (eq 13).
Generation of New Sulfur Ylides.
Treatment of cyclic b-chloro-substituted enones and chloropyrimidines with dimethylsulfoxonium methylide results in the formation of new sulfoxonium ylides.43-47 Dimethylsulfoxonium methylide also reacts with acid anhydride,48 acid chloride,49 isocyanate,50 and other activated carbonyl groups51,52 to generate new sulfur ylides for further reactions. This method has been used to prepare acylated stable ylides53 which can be converted to other products or further reacted with a second mole of the a,b-unsaturated carbonyl compounds (eqs 14-16).
Dimethylsulfoxonium methylide is an efficient methylene transfer reagent in reactions with terminal epoxides to provide the corresponding oxetanes (eq 20).10,62,63 The oxetanes can also be prepared from ketones or aldehydes with dimethylsulfoxonium methylide via double methylene transfer reactions.
Reaction with Other Functional Groups.
1. Corey, E. J.; Chaykovsky, M. JACS 1965, 87, 1353.
2. Traynelis, V. J.; McSweeney, J. V. JOC 1966, 31, 243.
3. Johnson, C. R. In Comprehensive Organic Chemistry; Barton, D. H. R., Ed.; Pergamon: Oxford, 1979; Vol. 3, p 247.
4. Schmidbaur, H.; Tronich, W. TL 1968, 51, 5335.
5. FF 1968, 1, 315.
6. Gololobov, Y. G.; Nesmeyanov, A. N.; Lysenko, V. P.; Boldeskul, I. E. T 1987, 43, 2609.
7. Radunz, H. E.; Orth, D.; Baumgarth, M.; Schliep, H. J.; Enenkel, H. J. U.S. Patent 4 309 441, 1982 (CA 1982, 96, 199 394s).
8. Corey, E. J.; Chaykovsky, M. OSC 1973, 5, 755.
9. Ng, J. S. SC 1990, 20, 1193.
10. Wicks, D. A.; Tirrell, D. A. J. Polym. Sci., Part A: Polym. Chem. 1990, 28, 573.
11. Schmidbaur, H. ACR 1975, 8, 62.
12. Merz, A.; Märkl, G. AG 1973, 85, 867.
13. Abarca, B.; Ballesteros, R.; Jones, G. JHC 1984, 21, 1585.
14. Richardson, K.; Whittle, P. J. U.S. Patent 4 518 604, 1985 (CA 1985, 103, 178 265y).
15. Ogilvie, K. K.; Nguyen-ba, N.; Hamilton, R. G. CJC 1984, 62, 1622.
16. Popp, F. D.; Watts, R. F. JHC 1978, 15, 675.
17. Kulkarni, B. S.; Rao, A. S. OPP 1978, 10, 73.
18. Anderson, M. W.; Jones, R. C. F. JCS(P1) 1986, 2, 205.
19. Kongkathip, B.; Sookkho, R.; Kongkathip, N. CL 1985, 1849.
20. Rosenberger, M.; Jackson, W.; Saucy, G. HCA 1980, 63, 1665.
21. Bouda, M.; Borredon, M. E.; Delmas, M.; Gaset, A. SC 1987, 17, 503.
22. Sinisterra, J. V.; Marinas, J. M.; Riquelme, F.; Arias, M. S. T 1988, 44, 1431.
23. Borredon, E.; Clavellinas, F.; Delmas, M.; Gaset, A.; Sinisterra, J. V. JOC 1990, 55, 501.
24. Crooks, P. A.; Sommerville, R. CI(L) 1984, 350.
25. Moody, C. J.; Beck, A. L.; Coates, W. J. TL 1989, 30, 4017.
26. Matsuda, A.; Ueda, T. CPB 1986, 34, 1573.
27. Herscovici, J.; Egron, M. J.; Antonakis, K. JCS(P1) 1986, 1297.
28. Martin, J. L.; Tou, J. S.; Reusch, W. JOC 1979, 44, 3666.
29. Bly, R. S.; Bly, R. K.; Shibata, T. JOC 1983, 48, 101.
30. Farcasiu, D. S 1972, 615.
31. Bravo, P.; Ticozzi, C. G 1979, 109, 169.
32. Salimbeni, A.; Manghisi, E.; Arnone, A. JHC 1988, 25, 943.
33. Bravo, P.; Ticozzi, C.; Maggi, D. CC 1976, 789.
34. Cambie, R. C.; Rutledge, P. S.; Strange, G. A.; Woodgate, P. D. H 1982, 19, 1501.
35. Abdel-Sayed, A. N.; Bauer, L. T 1988, 44, 1873.
36. Hoagland, S.; Morita, Y.; Bai, D. L.; Märki, H. P.; Kees, K.; Brown, L.; Heathcock, C. H. JOC 1988, 53, 4730.
37. Girijavallabham, V. M.; Ganguly, A. K.; Pinto, P. A.; Sarre, O. Z. BML 1991, 1, 349.
38. Koolpe, G. A.; Nelson, W. L.; Gioannini, T. L.; Angel, L.; Simon, E. J. JMC 1984, 27, 1718.
39. Sano, T.; Shuto, S.; Inoue, H. CPB 1985, 33, 3617.
40. Smith, A. B., III; Fukui, M. JACS 1987, 109, 1269.
41. Satyamurthy, N.; Berlin, K. D. PS 1984, 19, 113.
42. Ackland, M. J.; Gorden, J. F.; Hanson, J.; Ratcliffe, A. H. JCS(P1) 1988, 2009.
43. Chalchat, J. C.; Garry, R.; Michet, A.; Vessiere, R. CR(C) 1978, 286, 329.
44. Bradbury, R. H.; Gilchrist, T. L.; Rees, C. W. CC 1979, 528.
45. Niitsuma, S.; Sakamoto, T.; Yamanaka, H. H 1978, 10, 171.
46. Yamanaka, H.; Konno, S.; Sakamoto, T.; Niitsuma, S.; Noji, S. CPB 1981, 29, 2837.
47. Green, G. E.; Irving, E. Eur. Patent 35 969, 1981 (CA 1982, 96, 69 594w).
48. Johnson, C. R.; Rogers, P. E. JOC 1973, 38, 1798.
49. Truce, W. E.; Madding, G. D. TL 1966, 3681.
50. König, H.; Metzger, H. CB 1965, 98, 3733.
51. Nagao, Y.; Inoue, T.; Fujita, E.; Terada, S.; Shiro, M. T 1984, 40, 1215.
52. Nozaki, H.; Tunemoto, D.; Matubara, S.; Kondo, K. T 1967, 23, 545.
53. Speakman, P. R. H.; Robson, P. TL 1969, 1373.
54. Metzger, H.; König, H.; Seelert, K. TL 1964, 867.
55. Bravo, P.; Gaudiano, G.; Ticozzi, C.; Umani-Ronchi, A. CC 1968, 1311.
56. Kunieda, T.; Witkop, B. JOC 1970, 35, 3981.
57. Watson, C. R., Jr.; Pagni, R. M.; Dodd, J. R.; Bloor, J. E. JACS 1976, 98, 2551.
58. Nadir, U. K.; Koul, V. K. CC 1981, 417.
59. Nadir, U. K.; Sharma, R. L.; Koul, V. K. T 1989, 45, 1851.
60. Nadir, U. K.; Sharma, R. L.; Koul, V. K. JCS(P1) 1991, 2015.
61. Nadir, U. K.; Sharma, R. L.; Koul, V. K. IJC(B) 1989, 28B, 685.
62. Okuma, K.; Tanaka, Y.; Kaji, S.; Ohta, H. JOC 1983, 48, 5133.
63. Fitton, A. O.; Hill, J.; Jane, D. E.; Millar, R. S 1987, 1140.
64. Taylor, K. G.; Hobbs, W. E.; Clark, M. S.; Chaney, J. JOC 1972, 37, 2436.
65. Tewari, R. S.; Nagpal, D. K. JIC 1979, 56, 911.
66. Johnson, C. R.; Mori, K.; Nakanishi, A. JOC 1979, 44, 2065.
67. Nichols, D. E.; Woodard, R.; Hathaway, B. A.; Lowy, M. T.; Yim, G. K. W. JMC 1979, 22, 458.
68. Baker, W. R.; Martin, S. F. World Patent 92 00 972, 1992 (CA 1992, 116, 256 057s).
69. Mapelli, C.; Turocy, G.; Switzer, F. L.; Stammer, C. H. JOC 1989, 54, 145.
70. Landor, S. R.; Punja, N. JCS(C) 1967, 2495.
71. Minami, T.; Matsumoto, M.; Suganuma, H.; Agawa, T. JOC 1978, 43, 2149.
72. Rodriques, K. E. TL 1991, 32, 1275.
73. König, H.; Metzger, H.; Seelert, K. CB 1965, 98, 3712.
74. Sakakibara, T.; Sudoh, R.; Nakagawa, T. BCJ 1978, 51, 1189.
75. Radatus, B.; Williams, U.; Baer, H. H. Carbohydr. Res. 1986, 157, 242.
76. Donnelly, J. A.; O'Brien, S.; O'Grady, J. JCS(P1) 1974, 1674.
77. Uno, H.; Yayama, A.; Suzuki, H. T 1992, 48, 8353.
78. Elkik, E.; Imbeaux-Oudotte, M. BSF 1987, 861.
79. Elkik, E.; Imbeaux-Oudotte, M. TL 1985, 26, 3977.
80. Murphy, W. S.; Wattanasin, S. JCS(P1) 1981, 2920.
81. Beal, R. B.; Dombroski, M. A.; Snider, B. B. JOC 1986, 51, 4391.
82. Piers, E.; Banville, J.; Lau, C. K.; Nagakura, I. CJC 1982, 60, 2965.
83. Evans, D. A.; Hart, D. J.; Koelsch, P. M. JACS 1978, 100, 4593.
84. Nickisch, K.; Bittler, D.; Casals-Stenzel, J.; Laurent, H.; Nickolson, R.; Nishino, Y.; Petzoldt, K.; Wiechert, R. JMC 1985, 28, 546.
85. Geetha, P.; Narasimhan, K.; Swaminathan, S. TL 1979, 565.
86. Paquette, L. A.; Ewing, G. D.; Ley, S. V.; Berk, H. C.; Traynor, S. G. JOC 1978, 43, 4712.
87. Marshall, J. A.; Ellison, R. H. JOC 1975, 40, 2070.
88. Steinberg, N. G.; Rasmusson, G. H.; Reamer, R. A. JOC 1979, 44, 2294.
89. Takahashi, T.; Yamashita, Y.; Doi, T.; Tsuji, J. JOC 1989, 54, 4273.
90. Hamdouchi, C. TL 1992, 33, 1701.
91. Romo, D.; Romine, J. L.; Midura, W.; Meyers, A. I. T 1990, 46, 4951.
92. Bravo, P.; Gaudiano, G.; Ticozzi, C.; Umani-Ronchi, A. TL 1968, 4481.
93. Gaudiano, G.; Umani-Ronchi, A.; Bravo, P.; Acampora, M. TL 1967, 107.
94. Ide, J.; Kishida, Y. TL 1966, 1787.
95. Kaiser, C.; Trost, B. M.; Beeson, J.; Weinstock, J. JOC 1965, 30, 3972.
96. Lecadet, D.; Paquer, D.; Thuillier, A. CR 1973, 276, 875.
97. Toure, S. A.; Voglozin, A.; Degny, E.; Danion-Bougot, R.; Danion, D.; Pradere, J. P.; Toupet, L.; N'Guessan, Y. T. BSF 1991, 128, 574.
98. Metzger, H.; Seelert, K. ZN(B) 1963, 18B, 335.
99. Nadir, U. K.; Chaurasia, B. P.; Sharma, R. L. CL 1989, 2023.
100. Nadir, U. K.; Chaurasia, B. P. IJC(B) 1992, 31B, 189.
101. Seno, M.; Tsuchiya, S. JCS(D) 1977, 8, 751.
102. Weber, L. ZN(B) 1976, 31B, 780 (CA 1976, 85, 124 091e).
103. Weber, L.; Matzke, T.; Boese, R. CB 1990, 123, 739.
104. Porschke, K. R. CB 1987, 120, 425.
105. Yamamoto, Y. BCJ 1987, 60, 1189.
106. Lin, I. J. B.; Lai, H. Y. C.; Wu, S. C.; Hwan, L. JOM 1986, 306, C24.
107. Weber, L.; Lucke, E.; Boese, R. CB 1989, 122, 809.

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