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For previous use of cyclic or acyclic enol ethers as dienophiles for the IEDDAR with tetrazines see:
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Tebbe reagent: μ-Chlorobis(cyclopentadienyl)-(dimethylaluminium)-μ-methylenetitan ium, Representative general procedure: To a solution of the corresponding ester (1.04 mmol) in THF (12 ml) cooled at -40 °C is added Tebbe reagent (2.7 ml, 1.3 equiv, 0.5 M in toluene). After 30 min the temperature is raised to ambient over a period of 2 h. The mixture is then cooled to -10 °C and the reaction is quenched by the dropwise addition of NaOH (700 μl, 2 M solution). Reaction mixture is then allowed to warm to room temperature. The solution is then diluted with excess of ether and filtered through a pad of Celite. Solvent is removed under reduced pressure and the crude residue is directly diluted in dioxane (10 ml) and added to a solution of tetrazine 1 (203 mg, 1.0 mmol) in dioxane (10 ml). After 18 h at room temperature, volatiles are removed and the crude residue is purified on silica gel (hexane/AcOEt mixtures) to afford the desired products
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Tebbe reagent: μ-Chlorobis(cyclopentadienyl)-(dimethylaluminium)-μ-methylenetitan ium,. Tebbe F.N., Parshall G.W., and Reddy G.S. J. Am. Chem. Soc. 100 (1978) 3611-3613 Representative general procedure: To a solution of the corresponding ester (1.04 mmol) in THF (12 ml) cooled at -40 °C is added Tebbe reagent (2.7 ml, 1.3 equiv, 0.5 M in toluene). After 30 min the temperature is raised to ambient over a period of 2 h. The mixture is then cooled to -10 °C and the reaction is quenched by the dropwise addition of NaOH (700 μl, 2 M solution). Reaction mixture is then allowed to warm to room temperature. The solution is then diluted with excess of ether and filtered through a pad of Celite. Solvent is removed under reduced pressure and the crude residue is directly diluted in dioxane (10 ml) and added to a solution of tetrazine 1 (203 mg, 1.0 mmol) in dioxane (10 ml). After 18 h at room temperature, volatiles are removed and the crude residue is purified on silica gel (hexane/AcOEt mixtures) to afford the desired products
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Tebbe, F.N.1
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