图片来源：Org. Syn. 反应探索该反应在室温下反应即可，具有不错的底物实用性，底物中的二甲氨基、双键、三键等基团都能兼容，产率也都不错。图片来源：Org. Syn. 底物范围该方法已经在天然产物全合成中得到应用。通过偶联两个片段，可以顺利完成分子骨架的合成。（Org. Lett. 2007, 9, 2717–2719. Org. Lett. 2008, 10, 4955–4957.）图片来源：Org. Syn. 实验操作图片来源：Org. Syn. C. (5-(9-Borabicyclo[3.3.1]nonan-9-yl)pentyloxy)triethylsilane (3). An oven-dried, 200-mL, round-bottomed flask equipped with an argon inlet and a magnetic stirbar (octagonal, molded pivot ring, 25 mm length and 6 mm diameter) is purged with argon for 10 min. The open neck is capped with a rubber septum, and then a solution of 9-borabicyclo[3.3.1]nonane (9-BBN; 0.50 M in THF; 72 mL, 36 mmol, 1.0 equiv) (Note 11) is added via syringe. Next, triethyl(pent-4-enyloxy)silane (2) (7.21 g, 36.0 mmol, 1.0 equiv) is added via syringe over 3 min to the solution of 9-BBN. The reaction mixture is stirred for 3 h, at which time all of the starting olefin is consumed as determined by TLC analysis (pentane as the eluent; visualization with a KMnO4 stain; the olefin starting material has an Rf = 0.2) . This solution is used directly in the next step.D. (13-Chlorotridecyloxy)triethylsilane (4). An oven-dried, 1000-mL, three-necked, round-bottomed flask equipped with a thermometer inlet, a thermometer, a magnetic stir bar (octagonal, molded pivot ring, 40 mm length and 10 mm diameter), and an argon inlet is purged with argon for 10 min. Palladium(II) acetate (270 mg, 1.20 mmol, 0.040 equiv) (Note 12), tricyclohexylphosphine (673 mg, 2.40 mmol, 0.080 equiv) (Note 13), and tripotassium phosphate, monohydrate (K3PO4·H2O; 8.28 g, 36.0 mmol, 1.2 equiv) (Note 14) are added through the open neck of the flask. Then, the open neck is capped with a rubber septum, and the solution of (5-(9-borabicyclo[3.3.1]nonan-9-yl)-pentyloxy)triethylsilane (3) prepared in Step C (36 mmol, 1.2 equiv) is added to the flask via syringe, followed by the addition of 1-bromo-8-chlorooctane (1) (6.83 g, 30.0 mmol, 1.0 equiv). The resulting dark-brown heterogeneous reaction mixture is stirred vigorously at rt for 24 h. The progress of the reaction is followed by TLC analysis on SiO2 (25% CH2Cl2/hexanes as the eluent; visualization with a KMnO4 stain; the alkyl bromide starting material has an Rf = 0.5, and the cross-coupling product has an Rf = 0.4) . Next, the mixture is diluted with diethyl ether (200 mL) and filtered through a sintered glass funnel containing SiO2 (7.0 cm diameter 5.0 cm height). The SiO2 is washed with additional diethyl ether (200 mL), and the combined filtrate is concentrated by rotary evaporation (20 mmHg, 30 °C). The residue is purified by column chromatography on SiO2 (Note 15). The desired cross-coupling product 4 has Rf = 0.7 (TLC analysis on SiO2: 50% CH2Cl2/hexanes as eluent, visualization with KMnO4) (Note 5). The cross-coupling product is obtained as a pale-yellow oil (9.63–10.10 g, 92–96% yield) .
