烯基醚的合成基本上可以参考烯烃和醚这两种官能团的合成方法。

构建双键的方法合成烯基醚

实例一

消除反应制备烯基醚

A mixture of 0.01 mol 2-bromoethyl benzyl ether, 0.01mol(DBU), and THF (10 mL) was stirred intensely at 60 °C for 8 h. Subsequently cooled pentane (10 mL) was added and the mixture was left at 0 °C overnight. The salt precipitate was filtered and washed with 10 mL of tetrahydrofuran and pentane mixture (1:1). Volatile fractions were removed by distillation and benzyl vinyl ether was obtained in practically quantitative yield (purity>99%; GC).

Reference:J. Organomet. Chem., 2004,689, 2631-2367.

实例二

Tebbe试剂与酯反应制备烯基醚

The reactions were carried out under an inert atmosphere in the dark. The lactone (1.0 mmol) and dicyclopentadienyl-dimethyl titanocene (2.2 mmol) were dissolved in dry toluene, heated to 70°C and stirred for the given time. After completion the solvent was removed in vacuo and the residue purified by column chromatography (indicated conditions).

Reference: Org. Lett., 2013,15, 4948-4951.

实例三

Typical Procedure An oven-dried, two-necked round-bottomed flask fitted with a reflux condenser was charged with Pd(OAc)2 (56 mg, 0.25 mmol), dppp (205 mg, 0.50 mmol),4-bromoacetophenone (1; 5.05 g, 25 mmol), and ethylene glycol (40 mL). The flask was evacuated and back-filled three times with N2 and Et3N(9.6 mL, 75 mmol) was added via a syringe. The flask was immersed in an oilbath at 100 °C and stirred vigorously for 3-4 min until a bright yellow color developed, at which point BVE (8 mL, 75 mmol) was added via a syringe. After an appropriate time (1-3 h), the reaction was cooled and the crude reaction mixture was extracted with Et2O (3 × 100 mL). The combined extracts were concentrated in vacuo and the crude residue was purified by flash chromatography (hexanes-EtOAc-Et3N, 98:1:1). 3; yield: 4.63 g (85%).

Reference:Synthesis., 2010, 349-360.

实例四

Still反应制备烯基醚

To a solution of 4-bromo-3-fluorobenzaldehyde (1.00 g, 4.9 mmol) in dioxane (10.0 mL) was added to tributyl(1-ethoxyvinyl)stannane (1.7 mL, 5.2 mmol) and Pd(PPh3)2Cl2(0.069 g, 0.099 mmol). The resulting solution was purged with argon for 2 min,then sealed and heated (microwave) at 130 °C for 30 min. After cooling to 25°C, the reaction mixture was filtered through a plug of silica gel, eluting with EtOAc (80 mL). The filtrate was then concentrated in vacuo and chromatographically purified (silica gel, 0-30% EtOAc/hexanes) to provide4-(1-ethoxyvinyl)-3-fluorobenzaldehyde (0.881 g, 92% yield) as a light-yellow oil.

Reference:Synthesis., 2010, 349-360.