- Oxidative fragmentations of 2-(trimethylsilyl)ethyl sulfoxides - Routes to alkane-, arene-, and highly substituted 1-alkenesulfinyl chlorides
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The preparation of a collection of alkyl, aryl, and 1-alkenyl 2-(trimethylsilyl)ethyl sulfoxides is outlined, using mostly vinyltrimethylsilane or 2-(trimethylsilyl)ethanesulfenyl chloride (5) as key starting materials. The 2-(trimethylsilyl)ethyl group can be cleaved from many of the sulfoxides under oxidative fragmentation conditions using sulfuryl chloride and the reaction represents a new protocol for sulfinyl chloride synthesis. The method is suitable for most alkane- and arenesulfinyl chlorides (3), but is limited to highly substituted vinylic sulfinyl chlorides. 1-Alkenyl 2-(trimethylsilyl)ethyl sulfoxides with reduced double bond substitution (6, 7, 11) succumb to reactions involving chlorination of the double bond. The β-effect of silicon is invoked to explain the ability of the 2-(trimethylsilyl)ethyl group to induce C-S bond scission under the oxidative cleavage reaction conditions. A mechanism is offered to account for the role played by the β-silicon atom of the 2-(trimethylsilyl)ethyl group. Indeed, the silicon atom is self-sacrificial in that it diverts the course of the reaction from the usual α-carbon chlorination mode to one of oxidative cleavage, whereby the 2-(trimethylsilyl)ethyl group is lost. The overall reaction calls upon the ability of silicon atoms to donate electron density by hyperconjugation.
- Schwan, Adrian L.,Strickler, Rick R.,Dunn-Dufault, Robert,Brillon, Denis
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p. 1643 - 1654
(2007/10/03)
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- The reaction of 2-trimethylsilylethyl sulfoxides with sulfuryl chloride. A fragmentation route to sulfinyl chlorides
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Sulfinyl chlorides were prepared in good to excellent yields by reacting aryl or alkyl 2-trimethylsilylethyl sulfoxides with SO2Cl2.
- Schwan,Dufault
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p. 3973 - 3974
(2007/10/02)
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- 1-LITHIO-1-BENZENESULFINYL-2-TRIMETHYLSILYLETHANE AS A 2-TRIMETHYLSILYLVINYL ANION EQUIVALENT IN REACTIONS WITH ALHEDYDES, KETONES AND EPOXIDES
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Aldehydes, ketones and epoxides give adducts with 1-lithio-1-benzenesulfinyl-2-trimethylsilylethane which upon neutralization eliminate benezenesulfenic acid efficiently at 76 deg C to yield trans-3-(trimethylsilyl)allyl alcohols and trans-4-(trimethylsilyl)-3-alken-1-ols.
- Hsiao, C-N.,Shechter, H.
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p. 2371 - 2374
(2007/10/02)
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- Silicon-directed Elimination from β-Trimethylsilyl Sulphoxides and the Regiospecific Synthesis of Olefins
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The regiospecific formation of olefins by the thermal elimination of sulphenic acid from β-trimethylsilyl sulphoxides followed by protodesilylation is reported and the effect of the trimethylsilyl group on thermal elimination is discussed.
- Ochiai, Masahito,Tada, Shin-ichi,Sumi, Kenzo,Fujita, Eiichi
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p. 281 - 282
(2007/10/02)
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