Final Summary Report 表述.pdf

Final Summary Report 表述 (一) 加料过程中常用到的表述 1． 添加试剂 To a mixture (suspension/solution/slurry) of compound 12 (487 mg, 1 mmol) and o-phenylenediamine (648 mg, 6 mmol) in CH2Cl2 (15 mL) cooled to 0 was added ℃ DCC (226 mg, 1.1 mmol). Anhydrous lithium iodide (1.38 g, 10.3 mmol) was added in five portions (dropwise/in one portion/in portions/portionwise) to a stirred solution of compound 12 (10.93 g, 51.5 mmol) in CH2Cl2 (120 mL). A 3 L three-necked round bottom flask equipped with mechanical stirrer, addition funnel and thermometer (or Dean-Stock; drying tube) were charged with A (10 mL, 1 mol), B (2 g, 1 mol) and C (50 mL). 分批加入 in portions/portionwise 一次性加入 in one portion 滴加 dropwise A round-bottom flask was charged with compound 33 (1.75 g, 5.27 mmol), LiCl (1.17 g, 26.3 mmol), DMSO (100 mL) and H2O (378 μL). 2. 反应控温 A solution of compound 1 (10 g , 1 mole) in EtOAc (20 mL) was added dropwise (via addition funnel or syringe) to the above mixture at 10 ℃ (while maintaining gentle reflux; while keeping internal temperature between 10 ℃ – 30 ℃) under N2. 3. 催化量的试剂 Et3N (20 mL, 142 mmol) and a catalytic amount of DMAP were added to a solution of compound 1 (4.549 g, 46.4 mmol) in CH2CH2 (120 mL) at 0 ℃. 4. 气体保护 To a stirred –78 ℃ solution of trimethylsilylacetylene (4.44 g, 45.2 mmol) in THF (10 mL) under Argon was added dropwise n-butyllithium (1.6 M in hexane, 28.25 mL). 5. 通入气体 An ozone-enriched stream of oxygen was bubbled through a cold (-78 ℃) solution of compound 9a (128 mg, 0.409 mmol) in CH2Cl2 (5 mL) until it turned light blue. The solution was purged with argon at -78 ℃ for 10 min to remove excess O3. 6. 通过双针头导管加料 This mixture was added to a solution of compound 2 (3.00 g, 12.8 mmol) in THF (48 mL) via cannula over a period of 30 min. A solution of compound 29 (100 mg, 0.19 mmol, 1.0 equiv) in dry DMSO (0.5 mL) was cannulated under Ar to a vigorously stirred mixture of powdered potassium superoxide (62