Triethylsilyl hydrotrioxide

Miraz-Aghayan, M. Boukherroub, R. Bolourtchian, M. Hoseini, M. Tabar-Hydar, K., 7. Organomet. CherrL 2003, 678, 1. 

Ohshita, J., CherrL Lett. 2001, 1228. 

Preparative Methods addition of triethylsilane (2 equiv) to a cold (—78 °C), saturated methylene chloride solution of ozone (ca. 0.04 M) results in discharge of the color with formation of triethylsilyl hydrotrioxide within 45 s.  

Handling, Storage, and Precautions is prepared in solution immediately before use. In methylene chloride at —78 °C, the half-life of the reagent has been estimated to be a few minutes. Precautions appropriate for reactions which utilize or generate peroxides should be used. 

Alkene Oxidation Reactions. The reaction of triethylsilane with ozone and use of the intermediate triethylsilyl hydrotrioxide in oxidation reactions have been described. Initial oxidation reactions reported included the formation of the 9,10-endoperoxide from 9,10-dimethylanthracene (eq 1), and an allyUc hydroperoxide from 2,3-dimethyl-2-butene (eq 2). Researchers also observed a near-IR emission from triethylsilyl hydrotrioxide as it decomposed at —60°C, consistent with generation of singlet oxygen. Other workers have characterized triethylsilyl hydrotrioxide by NMR spectroscopy and and measured the kinetics of its decomposition in deuterated acetone.  

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Posner and coworkers reported that triethylsilyl hydrotrioxide is an efficient reagent for direct conversion of electron-rich alkenes to 1,2-dioxetanes 72 (equation 80) . 

A mechanism was proposed to account for the reaction of triethylsilyl hydrotrioxide with electron-rich alkenes as a dioxetane-forming process (route a equation 82) and with inactivated alkenes as a nondioxetane carbonyl-forming process (route b equation 83). 

Tricyclic trioxanes, synthesis, 282, 283 Tricyclohexylgermyl hydroperoxide, thermal decomposition, 822-3 Triethylsilane, oxidation, 807-8 Triethylsilyl hydrotrioxide... 

Reaction of triethylsilyl hydrotrioxide with electron-rich olefins to give dioxetanes that react intramolecularly with a keto group in the presence of t-butyldimethyl silyl triflateto afford 1,2,4-trioxanes also oxydative cleavage of alkenes. Also used in cleavage of olefins (see 1st edition)... 

In the case of an enol ether derivative (eq 5), reaction with triethylsilyl hydrotrioxide produced an intermediate dioxetane which was cleaved to give 3-phenylpropionaldehyde upon warming. In contrast, reaction of the same enol ether with photochem-ically generated singlet oxygen proceeded via an ene pathway. After hydrolysis, this gave an a , -unsaturated aldehyde in 37% yield. ... 

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