tert-Butanol → HCID 58930151, compound

HRID 1158083Notes

Reaction equation

HRID 1158083 reaction equation
[CH3:1][S:2]([C:5]1[CH:10]=[CH:9][C:8]([C:11]23[CH2:18][CH2:17][C:14](C(O)=O)([CH2:15][CH2:16]2)[CH2:13][CH2:12]3)=[CH:7][CH:6]=1)(=[O:4])=[O:3].C([N:24]([CH2:27]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:36])C=CC=CC=1.[C:46]([OH:50])([CH3:49])([CH3:48])[CH3:47]>[Cu]Cl.C1(C)C=CC=CC=1>[CH3:1][S:2]([C:5]1[CH:10]=[CH:9][C:8]([C:11]23[CH2:18][CH2:17][C:14]([NH:24][C:27](=[O:36])[O:50][C:46]([CH3:49])([CH3:48])[CH3:47])([CH2:15][CH2:16]2)[CH2:13][CH2:12]3)=[CH:7][CH:6]=1)(=[O:4])=[O:3]

Participants

7

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 20755042HCID 20755042, compound

Product 1

HCID 58930151HCID 58930151, compound

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 1140TolueneSolvent

Conditions

Temperature
50 °C

Procedure

To a flame-dried 100 mL round-bottomed flask equipped with magnetic stirring and argon inlet/outlet was added 4-(4-(methylsulfonyl)phenyl)bicyclo[2.2.2]octane-1-carboxylic acid (200 mg, 649 μmol, prepared by the method described in US Patent Application: 2004/0133011 and 5 mL of toluene. Triethylamine (0.10 mL, 713 μmol) was added followed by diphenylphosphoryl azide (0.2 mL, 713 μmol), and the reaction mixture warmed in a 50° C. oil bath for 30 min, then to 70° C. for 5 h. tert-Butanol (5 mL, 53 mmol) was then added, and the reaction mixture continued to stir in the 70° C. bath. After 20 h, copper (I) chloride (10 mg, 101 μmol) was added, and the reaction continued to stir for ca 1.5 d at 70° C. The reaction was removed from the oil bath and then poured thru a 1 cm pad of Celite. The Celite pad was washed with CH2Cl2, and the filtrate was concentrated in vacuo. CH2Cl2 (50 mL) was added to the filtrate, and the organic layer was washed with 1M NaOH (2×), sat'd NH4Cl, sat'd NaHCO3, and brine. The organic layer was then dried over MgSO4, filtered and concentrated in vacuo to give tert-butyl 4-(4-(methylsulfonyl)phenyl)bicyclo[2.2.2]octan-1-ylcarbamate (mass=170 mg). The crude reaction product was taken onto the next step without further purification.

Workup

  1. customTo a flame-dried 100 mL round-bottomed flask equipped
  2. customprepared by the method
  3. stirringto stir in the 70° C. bath
  4. stirringto stir for ca 1.5 d at 70° C
  5. customThe reaction was removed from the oil bath
  6. additionpoured thru a 1 cm pad of Celite
  7. washThe Celite pad was washed with CH2Cl2
  8. concentrationthe filtrate was concentrated in vacuo
  9. additionCH2Cl2 (50 mL) was added to the filtrate
  10. washthe organic layer was washed with 1M NaOH (2×)
  11. dry with materialThe organic layer was then dried over MgSO4
  12. filtrationfiltered
  13. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-3e772f07734f483ba36f63535a747297
Source dataset
uspto-grants-2010_10
Patent number
US07807700B2

Reaction notes

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