Sodium methylsulfinylmethylide
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| Sodium methylsulfinylmethylide | |
|---|---|
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| IUPAC name | Sodium methylsulfinylmethylide |
| Other names | sodium dimsylate, dimsylsodium, NaDMSYL |
| Identifiers | |
| Abbreviations | NaDMSO |
| CAS number | [15590-23-5] |
| Properties | |
| Molecular formula | C2H5NaOS |
| Molar mass | 100.13 |
| Solubility in water | Reactive |
| Solubility in DMSO | Soluble |
| Related compounds | |
| Related compounds | Dimethyloxosulfonium methylide |
| Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) Infobox disclaimer and references |
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Sodium methylsulfinylmethylide (also called NaDMSO) is the conjugate base of dimethyl sulfoxide. It has several uses in organic chemistry as a base and nucleophile.
Since the first publication in 1965 by Corey et al.[1], a large number of publications have described additional uses for this reagent.[2]
Contents |
[edit] Preparation
Sodium methylsulfinylmethylide is prepared by heating sodium hydride or sodium amide[3] in DMSO at 70 °C for 1 hr.
[edit] Applications
[edit] As a Base
The pKa of DMSO is 35, which leads NaDMSO to be a powerful Brønsted base. NaDMSO is used in the generation of phosphorus and sulfur ylides.[4] NaDMSO in DMSO is especially convenient in the generation of dimethyloxosulfonium methylide and dimethylsulfonium methylide.[1][5]
[edit] As a Nucleophile
[edit] Reaction with esters
NaDMSO will condense with esters (1) to form β-ketosulfoxides (2), which have been shown to be very useful synthetic intermediates.[6] Reduction of β-ketosulfoxides with aluminium amalgam gives methyl ketones (3).[7] Reaction with alkyl halides followed by elimination gives α,β-unsaturated ketones (4). Interestingly, β-ketosulfoxides can also be used in the Pummerer rearrangement to introduce nucleophiles alpha to a carbonyl (5).[8]
[edit] References
- ^ a b Corey, E. J.; Chaykovsky, M. J. Am. Chem. Soc. 1965, 87, 1345.
- ^ Durst, T. Adv. Org. Chem. 1969, 6, 285. (Review)
- ^ Kaiser, E. M.; Beard, R. D.; Hauser, C. R. J. Organomet. Chem. 1973, 59, 53.
- ^ Romo, D.; Myers, A. I. J. Org. Chem. 1992, 57, 6265.
- ^ Trost, B. M.; Melvin, L. S., Jr. Sulfur Ylides: Emerging Synthetic Intermediates; Academic: New York, 1975.
- ^ Ibarra, C. A.; Rodgríguez, R. C.; Monreal, M. C. F.; Navarro, F. J. G.; Tesoreo, J. M. J. Org. Chem. 1989, 54, 5620.
- ^ Swenton, J. S.; Anderson, D. K.; Jackson, D. K.; Narasimhan, L. J. Org. Chem. 1981, 46, 4825.
- ^ Isibashi, H.; Okada, M.; Komatsu, H.; Ikeda, M. S. Synthesis 1985, 643.
