Ethanol → HCID 145857641, compound

HRID 2216197Notes

Reaction equation

HRID 2216197 reaction equation
[CH3:1][Si:2]([CH3:27])([CH3:26])[CH2:3][CH2:4][O:5][C:6](=[O:25])[NH:7][C:8]1[CH:13]=[C:12]([CH3:14])[C:11](B2OC(C)(C)C(C)(C)O2)=[C:10]([NH2:24])[CH:9]=1.[C:28]([O:32][C:33](=[O:54])[NH:34][C:35]([C:37]1[S:38][C:39]([S:52][CH3:53])=[C:40]([S:42]([C:45]2[CH:50]=[CH:49][CH:48]=[C:47](Br)[CH:46]=2)(=[O:44])=[O:43])[CH:41]=1)=[NH:36])([CH3:31])([CH3:30])[CH3:29].C([O-])([O-])=O.[Na+].[Na+].C(O)C>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O.CCOC(C)=O.C1(C)C=CC=CC=1>[CH3:27][Si:2]([CH3:1])([CH3:26])[CH2:3][CH2:4][O:5][C:6](=[O:25])[NH:7][C:8]1[CH:9]=[C:10]([NH2:24])[C:11]([C:49]2[CH:48]=[CH:47][CH:46]=[C:45]([S:42]([C:40]3[CH:41]=[C:37]([C:35]([NH:34][C:33]([O:32][C:28]([CH3:29])([CH3:30])[CH3:31])=[O:54])=[NH:36])[S:38][C:39]=3[S:52][CH3:53])(=[O:43])=[O:44])[CH:50]=2)=[C:12]([CH3:14])[CH:13]=1

Participants

9

Reactant 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 57532218HCID 57532218, compoundHCID 145857672tert-butyl N-[4-(3-bromophenyl)sulfonyl-5-methylsulfanylthiophene-2-carboximidoyl]carbamate

Product 1

HCID 145857641HCID 145857641, compoundYield 55.5%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

A flask with a stirbar was charged with [3-amino-5-methyl-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-carbamic acid 2-trimethylsilanyl-ethyl ester ((Example 294: step e) 2.34 g, 5.96 mmol), {[4-(3-bromo-benzenesulfonyl)-5-methylsulfanyl-thiophen-2-yl]-imino-methyl}-carbamic acid tert-butyl ester ((Example 27: step c) 2.93 g, 5.96 mmol), aqueous Na2CO3 (2M, 11.9 mL, 23.8 mmol), ethanol (12 mL) and toluene (24 mL). The solution was sparged with argon for 10 min and Pd(PPh3)4 (689 mg, 0.6 mmol) was added. The biphasic solution was vigorously stirred under inert atmosphere at 80° C. for 16 h, then was cooled to rt. EtOAc (80 mL) and water (20 mL) were added and the layers were separated. The organic layer was washed with saturated NaHCO3 (2×20 mL), brine (20 mL) and was dried over sodium sulfate. Removal of the solvents in vacuo followed by column chromatography (85:15 DCM/EtOAc) of the residue yielded the title compound (2.24 g, 55%) as a light brown solid. 1H-NMR (CDCl3): δ 7.98 (ddd, 1H, J=1.3, 1.9, 7.8 Hz), 7.89 (m, 2H), 7.61 (t, 1H, J=7.7 Hz), 7.5 (dt, 1H, J=1.3, 7.7 Hz), 6.88 (s, 1H), 6.55 (d, 1H, J=1.7 Hz), 6.47 (s, 1H), 4.26 (m, 2H), 3.42 (s, 2H), 2.56 (s, 3H), 1.9 (s, 3H), 1.52 (s, 9H), 1.06 (m, 2H), 0.08 (s, 9H).

Workup

  1. customThe solution was sparged with argon for 10 min
  2. temperaturewas cooled to rt
  3. customthe layers were separated
  4. washThe organic layer was washed with saturated NaHCO3 (2×20 mL), brine (20 mL)
  5. dry with materialwas dried over sodium sulfate
  6. customRemoval of the solvents in vacuo

Sources & evidence

ORD record
ord-ef52491c304343e18555a8a10feeb7b0
Source dataset
uspto-grants-2006_09
Patent number
US07109354B2

Reaction notes

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