反应 #2487489

反应方程式

CuCN

LiCl

4-Iodobenzoic acid tert-butyl ester

Isopropyl magnesium chloride

iodododecanoic acid methyl ester

→

residue

收率 189.8%

4-(11-Methoxycarbonylundecyl)benzoic Acid tert-butyl Ester

收率 189.8%

溶剂

THF

THF

THF

反应条件

后处理

1. 1
   其他All glassware was dried
2. 2
   干燥THF was dried over molecular sieves
3. 3
   干燥LiCl was dried at 150° C. for 1 h
4. 4
   其他the solutions were transferred via syringe
5. 5
   其他The reaction was removed from the cold bath
6. 6
   温度to warm to rt
7. 7
   workup.WAITAfter 15 min
8. 8
   workup.ADDITIONtrimethylphosphite (0.62 ml) was added
9. 9
   workup.STIRRINGAfter stirring for 16 h
10. 10
    其他the reaction was quenched with sat. NH4Cl (6 ml)
11. 11
    workup.ADDITIONWater (100 ml) was added
12. 12
    萃取the solution was extracted with AcOEt (3×100 ml)
13. 13
    洗涤The organic extracts were pooled ant washed with water (100 ml) (some sat. NaCl and MeOH
14. 14
    workup.ADDITIONwas added
15. 15
    其他phase separation) and sat. NaCl (100 ml)
16. 16
    干燥dried over MgSO4
17. 17
    浓缩concentrated under vacuum

实验过程

All glassware was dried prior to use. THF was dried over molecular sieves. LiCl was dried at 150° C. for 1 h, then stored in a closed bottle. All reaction solutions were made under nitrogen, and the solutions were transferred via syringe. 4-Iodobenzoic acid tert-butyl ester (3 g, 9.9 mmol) was dissolved in THF (7.5 ml), and cooled to −20 to −30° C. Isopropyl magnesium chloride (10.9 mmol, 2M in THF) was added over 5 min, and the solution was stirred for 30 min. A solution of CuCN (0.97 g, 10.9 mmol) and LiCl (0.92 g, 21.7 mmol) in 7.5 ml THF was added. The reaction was removed from the cold bath and allowed to warm to rt. After 15 min, trimethylphosphite (0.62 ml) was added. After stirring for 5 min—iodododecanoic acid methyl ester (2.69 g, 7.89 mmol) was added in a solution of THF (5 ml). After stirring for 16 h, the reaction was quenched with sat. NH4Cl (6 ml). Water (100 ml) was added and the solution was extracted with AcOEt (3×100 ml). The organic extracts were pooled ant washed with water (100 ml) (some sat. NaCl and MeOH was added to aid phase separation) and sat. NaCl (100 ml), dried over MgSO4 and concentrated under vacuum to yield a two-phased residue (5.85 g). The residue was dissolved in AcOEt and added drop wise to a bed of silica in a glass filter (7.5 cm dia×3 cm). 200 ml of AcOEt was washed through the silica, and the filtrate was concentrated to yield a residue. This was dissolved in DCM (10 ml) and purified by flash chromatography (15 cm×40 mm, eluant 9:1 heptane/AcOEt). The relevant fractions were pooled and concentrated under vacuum. This was dissolved in 9:1 heptane/AcOEt (7 ml) and purified again by flash chromatography (15 cm×40 mm, eluant 9:1 heptane/AcOEt) to yield a colorless oil (185 mg).

来源