Tributylphosphine → HCID 22645055, compound

HRID 1976479Notes

Reaction equation

HRID 1976479 reaction equation
[N:1]([CH2:4][CH2:5][C:6]#[C:7][CH2:8][O:9][C:10]1[CH:15]=[CH:14][C:13]([S:16]([N:19]2[CH2:24][CH2:23][S:22][C:21]([CH3:26])([CH3:25])[CH:20]2[C:27]([O:29][CH3:30])=[O:28])(=[O:18])=[O:17])=[CH:12][CH:11]=1)=[N+]=[N-].C(P(CCCC)CCCC)CCC.C(#N)C.C(=O)=O.[C:50]([O:54][C:55](OC(OC(C)(C)C)=O)=[O:56])([CH3:53])([CH3:52])[CH3:51].C([O-])(O)=O.[Na+]>CCOCC.C1COCC1.C(OCC)(=O)C>[CH3:30][O:29][C:27]([CH:20]1[C:21]([CH3:26])([CH3:25])[S:22][CH2:23][CH2:24][N:19]1[S:16]([C:13]1[CH:14]=[CH:15][C:10]([O:9][CH2:8][C:7]#[C:6][CH2:5][CH2:4][NH:1][C:55]([O:54][C:50]([CH3:53])([CH3:52])[CH3:51])=[O:56])=[CH:11][CH:12]=1)(=[O:18])=[O:17])=[O:28]

Participants

9

Reactant 5

HCID 13831TributylphosphineHCID 90495Di-tert-butyl dicarbonateHCID 516892Sodium BicarbonateHCID 22645044HCID 22645044, compoundHCID 86587134Acetonitrile dry ice

Product 1

HCID 22645055HCID 22645055, compoundYield 40%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolvent2×HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-50 °C

Procedure

To a solution of 0.453 g (1.0 mmol) of methyl 4-({4-[(5-azido-2-pentynyl)oxy]phenyl}sulfonyl)-2,2-dimethyl-3-thiomorpholine carboxylate in 7 mL of ether and 1 mL of THF was dropwise added 0.275 mL (1.1 mmol) of tributylphosphine at room temperature. The reaction was stirred for 1h and then cooled to −50° C. (acetonitrile/dry ice bath). A solution of 0.24 g (1.1 mmol) of di-tert-butyldicarbonate in 3.5 mL of ether was added and stirred at −50° C. for 2h. Then 3.5 mL of saturated solution of NaHCO3 was added and the reaction was let warm to room temperature. The resulting mixture was diluted with ethyl acetate, washed with brine, dried over MgSO4, filtered and concentrated in vacuo. The residue was chromatographed on silica gel eluting with ethyl acetate:hexanes (1:6) to provide 0.21 g (40%) of methyl4-{[4-({5-[(tert-butoxycarbonyl)amino]-2-pentynyl}oxy)phenyl]sulfonyl}-2,2-dimethyl-3-thiomorpholine carboxylate as a colorless oil. Electrospray Mass Spec: 527.2 (M+H)+

Workup

  1. customat room temperature
  2. temperaturethe reaction was let warm to room temperature
  3. washwashed with brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was chromatographed on silica gel eluting with ethyl acetate:hexanes (1:6)

Sources & evidence

ORD record
ord-98acef9adfa14c9f987c36dcac958448
Source dataset
uspto-grants-2001_05
Patent number
US06225311B1

Reaction notes

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