Potassium Phosphate, Tribasic → HCID 70978021, compound

HRID 1626982Notes

Reaction equation

HRID 1626982 reaction equation
FC(F)(F)S(O[C:7]1[CH:19]=[CH:18][C:10]2[N:11]([CH2:14][CH:15]3[CH2:17][CH2:16]3)[N:12]=[N:13][C:9]=2[C:8]=1[Cl:20])(=O)=O.CC1(C)C(C)(C)OB([C:31]2[CH2:36][CH2:35][CH:34]([C:37]([O:39][CH3:40])=[O:38])[CH2:33][CH:32]=2)O1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].C(=O)(O)[O-].[Na+]>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.O1CCOCC1>[Cl:20][C:8]1[C:9]2[N:13]=[N:12][N:11]([CH2:14][CH:15]3[CH2:17][CH2:16]3)[C:10]=2[CH:18]=[CH:19][C:7]=1[C:31]1[CH2:36][CH2:35][CH:34]([C:37]([O:39][CH3:40])=[O:38])[CH2:33][CH:32]=1

Participants

8

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 516892Sodium BicarbonateHCID 66980107Methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohex-3-enecarboxylateHCID 86711985HCID 86711985, compound

Product 1

HCID 70978021HCID 70978021, compound

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

4-Chloro-1-(cyclopropylmethyl)-1H-benzotriazol-5-yl trifluoromethanesulfonate (0.22 g, 0.62 mmol), methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohex-3-ene-1-carboxylate (0.21 g, 0.77 mmol, 1.25 equiv), potassium phosphate (0.39 g, 1.8 mmol, 3 equiv) and tetrakis(triphenylphosphine)palladium(0) (71 mg, 0.062 mmol, 0.1 equiv) were combined in a degassed mixture of dioxane (5 mL) and water (0.5 mL) and placed into a preheated oil bath at 90° C. for 90 minutes. The mixture was cooled to ambient temperature, poured into sodium bicarbonate (75 mL, aqueous saturated) and extracted with ethyl acetate (2×75 mL). The combined organic extracts were dried with sodium sulfate, filtered and concentrated in vacuo. The residue was purified by silica gel gradient chromatography (100:0 to 25:75; hexanes:ethyl acetate), providing the titled compound as a colorless oil: 1H-NMR (400 MHz, d6-DMSO) δ 7.88 (1H, d, J=8.5 Hz), 7.41 (1H, d, J=8.5 Hz), 5.77-5.74 (1H, m), 4.61 (2H, d, J=7.7 Hz), 3.66 (3H, s), 3.37-3.32 (2H, m), 2.75-2.69 (1H, m), 2.49-2.30 (2H, m), 2.11-2.05 (1H, m), 1.84-1.76 (1H, m), 1.41-1.33 (1H, m), 0.57-0.53 (2H, m), 0.49-0.45 (2H, m) ppm; high resolution mass spectrometry (ES+) m/z 346.1316 [(M+H)+; calculated for C18H21ClN3O2: 346.1317].

Workup

  1. extractionextracted with ethyl acetate (2×75 mL)
  2. dry with materialThe combined organic extracts were dried with sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by silica gel gradient chromatography (100:0 to 25:75; hexanes:ethyl acetate)

Sources & evidence

ORD record
ord-2fdb90e982674924b890c281061009c7
Source dataset
uspto-grants-2014_07
Patent number
US08785482B2

Reaction notes

Loading…