Water → (S)-methyl 2-((tert-butoxycarbonyl)amino)-3-(4-(((perfluorobutyl)sulfonyl)oxy)-phenyl)propanoate

HRID 1050245Notes

Reaction equation

HRID 1050245 reaction equation
[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:14][C:15]1[CH:20]=[CH:19][C:18]([OH:21])=[CH:17][CH:16]=1)[C:10]([O:12][CH3:13])=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(N(CC)CC)C.[F:29][C:30]([F:45])([C:41]([F:44])([F:43])[F:42])[C:31]([F:40])([F:39])[C:32]([F:38])([F:37])[S:33](F)(=[O:35])=[O:34].O>CN(C1C=CN=CC=1)C.C(Cl)Cl>[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:14][C:15]1[CH:20]=[CH:19][C:18]([O:21][S:33]([C:32]([F:37])([F:38])[C:31]([F:39])([F:40])[C:30]([F:29])([F:45])[C:41]([F:44])([F:43])[F:42])(=[O:35])=[O:34])=[CH:17][CH:16]=1)[C:10]([O:12][CH3:13])=[O:11])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

7

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 67814Perfluoro-1-butanesulfonyl fluorideHCID 7019130Boc-Tyr-OMe

Product 1

HCID 90043941(S)-methyl 2-((tert-butoxycarbonyl)amino)-3-(4-(((perfluorobutyl)sulfonyl)oxy)-phenyl)propanoate

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

A stirred solution of (S)-methyl 2-((tert-butoxycarbonyl)amino)-3-(4-hydroxyphenyl)propanoate (1.257 g, 4.26 mmol), DMAP (26 mg, 0.213 mmol), and triethylamine (0.71 mL, 0.51 g, 5.11 mmol) in anhydrous DCM (15 mL) was cooled to 0° C. Then nonafluorobutanesulfonyl fluoride (0.82 mL, 1.41 g, 4.68 mmol) was added in one portion. The mixture was allowed to warm and stirred at room temperature. After 18 hours, the mixture was poured into water (80 mL) and extracted with DCM (2×100 mL). The combined organic layers were washed with brine (50 mL), dried over sodium sulfate, and concentrated under reduced pressure. The resultant residue was chromatographed using a Biotage™ 50 g silica gel cartridge by eluting with 0-10% EtOAc in 1:1 Hexane/DCM over 10 column volumes. The product fractions were combined and concentrated under reduced pressure to give the desired product as a clear, colorless oil. LC-MS: calculated for C19H20F9NO7S 577.08, observed m/e: 478.14 (M+H with loss of BOC)+ (Rt 2.67/4 min).

Workup

  1. temperatureto warm
  2. extractionextracted with DCM (2×100 mL)
  3. washThe combined organic layers were washed with brine (50 mL)
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe resultant residue was chromatographed
  7. washby eluting with 0-10% EtOAc in 1:1 Hexane/DCM over 10 column volumes
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-3135657f918b4e79a8991f09678a34af
Source dataset
uspto-grants-2016_07
Patent number
US09382243B2

Reaction notes

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