2,5-Bis(trimethylsilyloxy)furan1

[77220-06-5]  · C10H20O3Si2  · 2,5-Bis(trimethylsilyloxy)furan  · (MW 244.44)

(diene for use in cycloadditions;3 building block for quinones3 and heterocycles4-6)

Physical Data: bp 42-43 °C/0.01 mmHg.

Solubility: insol H2O; sol aprotic organic solvents.

Preparative Methods: readily prepared by the reaction of Succinic Anhydride, Triethylamine, Zinc Chloride, and Chlorotrimethylsilane in MeCN (eq 1). It can also be prepared in 66% yield using succinic anhydride, Trimethylsilyl Trifluoromethanesulfonate and triethylamine.2

Handling, Storage, and Precautions: very unstable to air and moisture.

Cycloadditions.

The title reagent is very reactive in Diels-Alder reactions, affording adducts with Dimethyl Acetylenedicarboxylate and Ethyl Acrylate in good to excellent yields. The resulting adducts can be desilylated with Sodium Fluoride in wet acetonitrile (eq 2).3

2,5-Bis(trimethylsilyloxy)furan also reacts with tetrachlorocyclopropene in carbon tetrachloride for 3 days to afford a bicyclic adduct in 33% yield (eq 3).4

Nucleophilic Additions.

2,5-Bis(trimethylsilyloxy)furan reacts with carbonyl compounds in the presence of a Lewis acid to form an anhydride which upon workup affords a dilactone (eq 4). This one-step procedure constitutes a facile entry to the 3,7-dioxabicyclo[3.3.0]octane system.5 This reaction is successful with both aldehydes and ketones.

2,5-Bis(trimethylsilyloxy)furan reacts with methyl vinyl ketone to produce a novel diketo acid (eq 5). This reaction may be conducted either thermally or in the presence of a Lewis acid such as Titanium(IV) Chloride at -78 °C.6


1. Fieser, M. A. FF, 10, 45.
2. Frick, U.; Simchen, G. LA 1987, 839.
3. Brownbridge, P.; Chan, T.-K. TL 1980, 21, 3423.
4. Seitz, G.; Van Gemmern, R. CZ 1987, 111, 209.
5. Brownbridge, P.; Chan, T.-K. TL 1980, 21, 3427.
6. Brownbridge, P.; Chan, T.-K. TL 1980, 21, 3431.

George A. Kraus

Iowa State University, Ames, IA, USA



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