- Mechanisms of Hydrolysis of (Trimethylsilyl)methanesulfonyl Chloride. Sulfene-Enamine Reactions in Water
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Kinetic, product analysis, and deuteration experiments are consistent with the following mechanisms of hydrolysis of (trimethylsilyl)methanesulfonyl chloride (1) (in 0.01 M KCl at 1 deg C): (a) pH /= 10.0, attack of hydroxide anion (i) at silicon to yield sulfene (5) and (ii) at an α-hydrogen to form (trimethylsilyl)sulfene (4), in each case followed by trapping of the sulfene to give either methanesulfonate (3) or (trimethylsilyl)methanesulfonate (6) salts.Aqueous potassium fluoride catalyzes the hydrolysis of 1 with formation of the methanesulfonate 3, evidently by way of silicophilic attack of fluoride anion on 1 with formation of sulfene (5).Reaction of 1 with an enamine 7 in water (at pH 8 or 9), with or without fluoride, gives two characteristic sulfene-enamine products, (i) the four-membered cycloadduct 8 and (ii) the methylsulfonyl aldehyde 9.The same or related products are also obtained from methanesulfonyl, 2-propanesulfonyl, and phenylmethanesulfonyl chlorides and enamines in water (at pH 9).Hydrolysis of 1 is also catalyzed by aniline or triethylamine evidently giving 5.
- King, James F.,Lam, Joe Y. L.
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p. 3429 - 3434
(2007/10/02)
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- New Synthetic Methods, 10. - β-Ketosulfones, Useful Ethylenediide Equivalents: The Synthesis of Unsaturated Carboxylic Acids
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α-Alkyl-thiolated cycloalkanones are, after oxidation to sulfones, ring-opened by halogenation to yield α-halosulfones.Ramberg-Baecklund rearrangement forms unsaturated carboxylic acids.The position of the newly formed double bond is fixed by the ring siz
- Scholz, Dieter
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p. 264 - 272
(2007/10/02)
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