Triphenylphosphine → tert-Butyl [[6-[(4-chlorophenylsulfonyl)(2,5-difluorophenyl)methyl]pyridin-3-yl]methyl]-N-(tert-butoxycarbonyl)carbamate

HRID 2080403Notes

Reaction equation

HRID 2080403 reaction equation
N(C(OC(C)C)=O)=NC(OC(C)C)=O.[Cl:15][C:16]1[CH:21]=[CH:20][C:19]([S:22]([CH:25]([C:34]2[CH:39]=[C:38]([F:40])[CH:37]=[CH:36][C:35]=2[F:41])[C:26]2[CH:31]=[CH:30][C:29]([CH2:32]O)=[CH:28][N:27]=2)(=[O:24])=[O:23])=[CH:18][CH:17]=1.[NH:42]([C:50]([O:52][C:53]([CH3:56])([CH3:55])[CH3:54])=[O:51])[C:43]([O:45][C:46]([CH3:49])([CH3:48])[CH3:47])=[O:44].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CCCCCC.O.O1CCCC1>[C:53]([O:52][C:50](=[O:51])[N:42]([CH2:32][C:29]1[CH:28]=[N:27][C:26]([CH:25]([S:22]([C:19]2[CH:18]=[CH:17][C:16]([Cl:15])=[CH:21][CH:20]=2)(=[O:23])=[O:24])[C:34]2[CH:39]=[C:38]([F:40])[CH:37]=[CH:36][C:35]=2[F:41])=[CH:31][CH:30]=1)[C:43]([O:45][C:46]([CH3:47])([CH3:48])[CH3:49])=[O:44])([CH3:56])([CH3:55])[CH3:54]

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 279800Di-tert-butyl IminodicarboxylateHCID 230285882-[(4-Chlorophenylsulfonyl)-(2,5-difluorophenyl)methyl]-5-(hydroxymethyl)pyridine

Product 1

HCID 59750714tert-Butyl [[6-[(4-chlorophenylsulfonyl)(2,5-difluorophenyl)methyl]pyridin-3-yl]methyl]-N-(tert-butoxycarbonyl)carbamateYield 32%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

Under a nitrogen atmosphere, diisopropyl azodicarboxylate (128 μl, 0.653 mmol) was added to a tetrahydrofuran (5 ml) solution of the 2-[(4-chlorophenylsulfonyl)(2,5-difluorophenyl)methyl]-5-(hydroxymethyl)pyridine (178 mg, 0.435 mmol) obtained in Example 43, di-t-butyl iminodicarboxylate (142 mg, 0.653 mmol) and triphenylphosphine (171 mg, 0.653 mmol). The resulting mixture was stirred at room temperature for 5 hours. Water was added to the reaction mixture, followed by extraction with ethyl acetate. The organic layer was washed sequentially with water and brine. The resulting organic layer was dried over sodium sulfate and then, concentrated under reduced pressure. The residue thus obtained was subjected to flash silica gel column chromatography, and the fraction obtained from the hexane:ethyl acetate=4:1 eluate was concentrated under reduced pressure to give the title compound (78 mg, 0.128 mmol, 32%) as a colorless oil.

Workup

  1. extractionfollowed by extraction with ethyl acetate
  2. washThe organic layer was washed sequentially with water and brine
  3. dry with materialThe resulting organic layer was dried over sodium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customThe residue thus obtained
  6. concentrationethyl acetate=4:1 eluate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-41160beeaf004f4fac1b8d4fda854aad
Source dataset
uspto-grants-2011_04
Patent number
US07932271B2

Reaction notes

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