3-Bromo-1-(trimethylsilyl)-1-propyne may be used in the preparation of tetrahydroisoquinoline-3-carboxylic acid derivatives. It may be used as reagent for the alkylation of dianion of β-keto esters at γ-carbon. It may be employed in the preparation of terminal conjugated enynes and allenic alcohols.
The general procedure for the synthesis of 3-bromo-1-trimethylsilyl-1-propyne from trimethylsilylpropargyl alcohol was as follows: To a solution of anhydrous dichloromethane (46.0 mL) containing triphenylphosphine (9.735 g, 37.11 mmol) under nitrogen atmosphere, bromine (5.438 g, 34.03 mmol) was slowly added at 0 °C. After 30 min of reaction, when the color of the solution changed from orange to white, trimethylsilylpropynol (3.960 g, 30.93 mmol) was slowly added. The reaction mixture was continued to be stirred for 1 h, followed by washing with water (3 × 30 mL) and 10% aqueous hydrochloric acid (2 × 20 mL) sequentially. The aqueous layer was extracted with ethyl acetate (3 x 20 mL) and the combined organic layers were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography using hexane as eluent to afford 3-bromo-1-trimethylsilyl-1-propyne in 70% yield (4.125 g, 21.6 mmol).
[1] Angewandte Chemie - International Edition, 2014, vol. 53, # 31, p. 8122 - 8126
[2] Chemistry - A European Journal, 2011, vol. 17, # 49, p. 13692 - 13696
[3] Tetrahedron, 1996, vol. 52, # 35, p. 11601 - 11624
[4] Bioorganic and Medicinal Chemistry Letters, 2009, vol. 19, # 21, p. 6127 - 6130
[5] Bulletin de la Societe Chimique de France, 1993, vol. 130, # 2, p. 154 - 159
