t-Butyldimethylsilyl Hydroperoxide-Mercury(II) Trifluoroacetate

t-BuMe2SiOOH + Hg(CF3CO2)2

[78957-19-4]  · C6H16O2Si  · t-Butyldimethylsilyl Hydroperoxide-Mercury(II) Trifluoroacetate  · (MW 148.28) (Hg(CF3CO2)2)

[13257-51-7]  · C4F6HgO4  · t-Butyldimethylsilyl Hydroperoxide-Mercury(II) Trifluoroacetate  · (MW 426.62)

(peroxymercuration of alkenes1)

Physical Data: (CF3CO2)2Hg: mp 171-173 °C; t-BuMe2SiOOH: mp -8 °C, bp 20-35 °C.

Solubility: (CF3CO2)2Hg: sol THF, DME, dioxane; insol hexane; t-BuMe2SiOOH: sol most common organic solvents.

Form Supplied in: (CF3CO2)2Hg: white, hygroscopic crystals; t-BuMe2SiOOH: colorless liquid. Widely available.

Handling, Storage, and Precautions: acute poison. (CF3CO2)2Hg is easily absorbed through the skin and is corrosive. Exposure to all mercury compounds is to be strictly avoided. Releases toxic Hg fumes when heated to decomposition. Protect from light. t-Butyldimethylsilyl hydroperoxide is a strong oxidant, and reacts readily with traces of metals.

The title hydroperoxide, in combination with (CF3CO2)2Hg, effects peroxymercuration of alkenes. The corresponding intermediate is then reduced with Sodium Borohydride to furnish an epoxide (eq 1).1 In contrast to the OH-directed epoxidation of allylic alcohols, this method appears to provide an avenue to the epoxy alcohols of opposite relative configuration (2-cyclopenten-1-ol and 2-cyclohexen-1-ol have been employed to demonstrate this stereoselectivity).1

Similarly, a mixture of t-BuMe2SiOOH and (AcO)2Hg has been reported to promote ring opening of cyclopropanes, giving the corresponding mercurated peroxides.2

Related Reagents.

Mercury(II) Acetate; Mercury(II) Trifluoroacetate.

1. Corey, E. J.; Schmidt, G.; Shimoji, K. TL 1983, 24, 3169.
2. Bloodworth, A. J.; Chan, K. H.; Cooksey, C. J.; Hargreaves, N. JCS(P1) 1991, 1923.

Pavel Kočovský

University of Leicester, UK

Copyright 1995-2000 by John Wiley & Sons, Ltd. All rights reserved.