Carbon Dioxide → HCID 86697940, compound

HRID 872167Notes

Reaction equation

HRID 872167 reaction equation
[C:1]([C:5]1[CH:17]=[CH:16][C:8]([CH2:9][NH:10][C:11](=[O:15])[N:12]([CH3:14])[CH3:13])=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].C([Li])(C)(C)C.[C:23](=[O:25])=[O:24]>C1COCC1>[C:1]([C:5]1[CH:6]=[CH:7][C:8]([CH2:9][NH:10][C:11]([N:12]([CH3:13])[CH3:14])=[O:15])=[C:16]([CH:17]=1)[C:23]([OH:25])=[O:24])([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 280Carbon DioxideHCID 69029937HCID 69029937, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 86697940HCID 86697940, compoundYield 80%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

A 500-mL, three-neck, round-bottomed flask equipped with a magnetic stirrer, addition funnel and thermocouple was purged with nitrogen and charged with 107a (9.36 g, 40.0 mmol) and THF (120 mL). The reaction was cooled to −70° C. and t-butyllithium (1.7 M in pentane, 56 mL, 95.2 mmol) was added dropwise. The reaction was allowed to warm to −45 to −35° C. for 0.5 h and then cooled back down to −78° C. The reaction was then cannulated into a 1-L, three-neck, round-bottomed flask which was filled with ˜100-200 g of dry ice under a flow of nitrogen. The mixture was warmed to room temperature and then concentrated under reduced pressure to dryness. Water (250 mL) and hexanes (250 mL) were added and the solution shaken. The aqueous layer was separated and extracted with methyl t-butyl ether ((150 mL). The aqueous layer was separated and then filtered through Cellpure P65 to clarify it. The aqueous filtrate was acidified with 20 mL of 12.1 M hydrochloric acid and stirred at ambient temperature overnight. After this time, the aqueous solution was decanted off, and the remaining solid was dried overnight under vacuum to afford an 80% yield of 107b (8.91 g) as a tan solid: 1H NMR (300 MHz, DMSO-d6) δ 12.97 (br s, 1H), 7.80 (d, 1H, J=2.1 Hz), 7.56 (dd, 1H, J=6.0, 2.1 Hz), 7.32 (d, 1H, J=8.1 Hz), 6.78 (t, 1H, J=5.7 Hz), 4.46 (d, 2H, J=5.7 Hz), 2.82 (s, 6H), 1.28 (s, 9H).

Workup

  1. customA 500-mL, three-neck, round-bottomed flask equipped with a magnetic stirrer, addition funnel
  2. customthermocouple was purged with nitrogen
  3. temperatureto warm to −45 to −35° C. for 0.5 h
  4. temperaturecooled back down to −78° C
  5. temperatureThe mixture was warmed to room temperature
  6. concentrationconcentrated under reduced pressure to dryness
  7. additionWater (250 mL) and hexanes (250 mL) were added
  8. customThe aqueous layer was separated
  9. extractionextracted with methyl t-butyl ether ((150 mL)
  10. customThe aqueous layer was separated
  11. filtrationfiltered through Cellpure P65
  12. stirringstirred at ambient temperature overnight
  13. customAfter this time, the aqueous solution was decanted off
  14. customthe remaining solid was dried overnight under vacuum

Sources & evidence

ORD record
ord-b7d6692a571a4054a812de25275cc0d8
Source dataset
uspto-grants-2015_03
Patent number
US08975260B2

Reaction notes

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