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Sodium methylsulfinylmethylide



Sodium methylsulfinylmethylide
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

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]

Additional recommended knowledge

Contents

Preparation

Sodium methylsulfinylmethylide is prepared by heating sodium hydride or sodium amide[3] in DMSO at 70 °C for 1 hr.

Applications

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]

As a Nucleophile

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]

References

  1. ^ a b Corey, E. J.; Chaykovsky, M. J. Am. Chem. Soc. 1965, 87, 1345.
  2. ^ Durst, T. Adv. Org. Chem. 1969, 6, 285. (Review)
  3. ^ Kaiser, E. M.; Beard, R. D.; Hauser, C. R. J. Organomet. Chem. 1973, 59, 53.
  4. ^ Romo, D.; Myers, A. I. J. Org. Chem. 1992, 57, 6265.
  5. ^ Trost, B. M.; Melvin, L. S., Jr. Sulfur Ylides: Emerging Synthetic Intermediates; Academic: New York, 1975.
  6. ^ Ibarra, C. A.; Rodgríguez, R. C.; Monreal, M. C. F.; Navarro, F. J. G.; Tesoreo, J. M. J. Org. Chem. 1989, 54, 5620.
  7. ^ Swenton, J. S.; Anderson, D. K.; Jackson, D. K.; Narasimhan, L. J. Org. Chem. 1981, 46, 4825.
  8. ^ Isibashi, H.; Okada, M.; Komatsu, H.; Ikeda, M. S. Synthesis 1985, 643.
 
This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Sodium_methylsulfinylmethylide". A list of authors is available in Wikipedia.
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