HCID 68637794, compound → (tert-Butoxycarbonylmethyl-{4-[2,7-difluoro-9-hydroxy-3,6-bis-(2-methoxyethoxymethoxy)-9H-xanthen-9-yl]-2-hydroxy-phenyl}-amino)-acetic acid tert-butyl ester

HRID 2357129Notes

Reaction equation

HRID 2357129 reaction equation
[C:1]([O:5][C:6](=[O:62])[CH2:7][N:8]([C:17]1[CH:22]=[CH:21][C:20]([C:23]2([OH:53])[C:36]3[CH:35]=[C:34]([F:37])[C:33]([O:38][CH2:39][O:40][CH2:41][CH2:42][O:43][CH3:44])=[CH:32][C:31]=3[O:30][C:29]3[C:24]2=[CH:25][C:26]([F:52])=[C:27]([O:45][CH2:46][O:47][CH2:48][CH2:49][O:50][CH3:51])[CH:28]=3)=[CH:19][C:18]=1[O:54]CC1C=CC=CC=1)[CH2:9][C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])([CH3:4])([CH3:3])[CH3:2]>C(O)C.CCOC(C)=O.[Pd]>[C:13]([O:12][C:10](=[O:11])[CH2:9][N:8]([CH2:7][C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:62])[C:17]1[CH:22]=[CH:21][C:20]([C:23]2([OH:53])[C:36]3[CH:35]=[C:34]([F:37])[C:33]([O:38][CH2:39][O:40][CH2:41][CH2:42][O:43][CH3:44])=[CH:32][C:31]=3[O:30][C:29]3[C:24]2=[CH:25][C:26]([F:52])=[C:27]([O:45][CH2:46][O:47][CH2:48][CH2:49][O:50][CH3:51])[CH:28]=3)=[CH:19][C:18]=1[OH:54])([CH3:16])([CH3:15])[CH3:14]

Participants

5

Reactant 1

HCID 68637794HCID 68637794, compound

Product 1

HCID 68638322(tert-Butoxycarbonylmethyl-{4-[2,7-difluoro-9-hydroxy-3,6-bis-(2-methoxyethoxymethoxy)-9H-xanthen-9-yl]-2-hydroxy-phenyl}-amino)-acetic acid tert-butyl esterYield 78.4%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 14 (956 mg, 1.1 mmol) in 95% ethanol (25 mL) and EtOAc (25 mL) was added 10% Pd/C (130 mg). The resulting mixture was stirred at room temperature overnight under H2 (1 atm). The catalyst was then removed by filtration and, after evaporation to dryness, the crude product was purified by flash column chromatography, eluting with 40% EtOAc in hexane (with 0.1% Et3N) to yield 671 mg (78%) of 15 as a light yellow oil. Rf=0.3 (in 40% EtOAc/hexane); 1H NMR (300 MHz, CDCl3) δ 8.1 (s, 1H), 7.18 (d, 1H, J=8.0 Hz), 6.95 (d, 2H, J=7.2 Hz), 6.69 (m, 3H), 6.57 (m, 1H), 5.28 (s, 4H), 4.94 (s, 1H), 3.85 (m, 4H), 3.69 (s, 4H), 3.57 (m, 4H), 3.38 (s, 6H), 1.41 (s, 18H); 13C NMR (75 MHz, CDCl3) δ 171.2, 153.8, 150.6, 147.4, 146.5, 144.8, 144.4, 144.2, 136.3, 126.3, 119.6, 116.7, 116.6, 116.1, 115.8, 115.5, 105.9, 94.6, 81.9, 71.4, 68.0, 59.0, 56.9, 43.1, 27.9; 19F NMR (282 MHz, CDCl3) δ −140.4 (dd, 2 F); mass spectrum, calculated for C46H55F2NO13 (M−17) 761.3, Found 761.7.

Workup

  1. customThe catalyst was then removed by filtration
  2. customafter evaporation to dryness
  3. customthe crude product was purified by flash column chromatography
  4. washeluting with 40% EtOAc in hexane (with 0.1% Et3N)

Sources & evidence

ORD record
ord-e93c4db7be3a4944a0d52369228c6053
Source dataset
uspto-grants-2010_07
Patent number
US07759459B2

Reaction notes

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