反应 #1519166

反应方程式

DPPA

5(S)-hydroxy-5,6,7,8-tetrahydro-naphthalene-2-carboxylic acid methyl ester

DBU

→

title compound

methyl (R)-5-azido-5,6,7,8-tetrahydro-naphthalene-2-carboxylate

溶剂

toluene

反应条件

后处理

1. 1
   其他To a 500 mL three-neck round-bottomed flask equipped with argon inlet/outlet
2. 2
   温度The reaction mixture was cooled in a ice-salt bath
3. 3
   其他was kept below 1° C
4. 4
   workup.STIRRINGthe mixture stopped stirring because a precipitate
5. 5
   其他had formed
6. 6
   workup.STIRRINGStirring
7. 7
   workup.STIRRINGthe reaction mixture was stirred at RT for another 11 h
8. 8
   其他The reaction contents
9. 9
   workup.ADDITIONwere poured into a 2 L sep funnel
10. 10
    其他the lower dark-brown layer was removed
11. 11
    workup.ADDITIONWater (250 mL) was added to the remaining top layer
12. 12
    萃取the mixture was extracted with Et2O (3×250 mL)
13. 13
    洗涤The combined organic layers were washed with 1 M H3PO4, water
14. 14
    干燥The organic layer was dried over MgSO4
15. 15
    过滤filtered
16. 16
    浓缩concentrated in vacuo
17. 17
    其他Purification by silica gel chromatography (330 g Isco Redisep® column, 1:1 hexane-CH2Cl2) of the crude material

实验过程

To a 500 mL three-neck round-bottomed flask equipped with argon inlet/outlet, thermometer, and magnetic stirring was added 5(S)-hydroxy-5,6,7,8-tetrahydro-naphthalene-2-carboxylic acid methyl ester (29 g, 140 mmol) in 280 mL of toluene. The reaction mixture was cooled in a ice-salt bath, and DPPA (36 mL, 170 mmol, Aldrich) was added (internal temp.=−4° C.). DBU (25 mL, 170 mmol, Aldrich) was added over 10 min at such a rate that the internal temperature was kept below 1° C. The ice in the bath was allowed to melt, and the reaction continued for 12 h during which time the mixture stopped stirring because a precipitate had formed. Stirring was resumed, and the reaction mixture was stirred at RT for another 11 h. The reaction contents were poured into a 2 L sep funnel, and the lower dark-brown layer was removed. Water (250 mL) was added to the remaining top layer, and the mixture was extracted with Et2O (3×250 mL). The combined organic layers were washed with 1 M H3PO4, water, satd NaHCO3, and brine. The organic layer was dried over MgSO4, filtered and concentrated in vacuo. Purification by silica gel chromatography (330 g Isco Redisep® column, 1:1 hexane-CH2Cl2) of the crude material provided the title compound. MS (+ion ESI) m/z=232 (MH+).

来源