Potassium Carbonate → 1443377-33-0

HRID 1473368Notes

Reaction equation

HRID 1473368 reaction equation
[CH:1]1(B(O)O)[CH2:3][CH2:2]1.Br[C:8]1[CH:13]=[CH:12][C:11](I)=[CH:10][C:9]=1[O:15][CH3:16].C(=O)([O-])[O-].[K+].[K+].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1.B1([B:66]2[O:70][C:69]([CH3:72])([CH3:71])[C:68]([CH3:74])([CH3:73])[O:67]2)OC(C)(C)C(C)(C)O1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>O1CCOCC1.CCCCCCC.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH:1]1([C:11]2[CH:12]=[CH:13][C:8]([B:66]3[O:67][C:68]([CH3:73])([CH3:74])[C:69]([CH3:71])([CH3:72])[O:70]3)=[C:9]([O:15][CH3:16])[CH:10]=2)[CH2:3][CH2:2]1

Participants

11

Reactant 6

HCID 11430Potassium CarbonateHCID 62657Potassium Phosphate, TribasicHCID 2733548Bis(pinacolato)diboraneHCID 2760897Cyclopropylboronic acidHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 121872021-Bromo-4-iodo-2-methoxybenzene

Product 1

HCID 665215481443377-33-0Yield 28.7%

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 178418807HCID 178418807, compoundCatalystHCID 8900HeptaneSolvent2×HCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

A solution of PdCl2(dppf)-CH2Cl2 adduct (1.391 g, 1.703 mmol), cyclopropylboronic acid (4.39 g, 51.1 mmol), 1-bromo-4-iodo-2-methoxybenzene (10.66 g, 34.1 mmol), and potassium carbonate (18.83 g, 136 mmol) in 100 mL dioxane/50 mL water was heated to 120° C. for 8 hours. LC/MS showed mostly product, so the reaction mixture was diluted with heptane and was washed with saturated NaHCO3 solution. The organics were dried over MgSO4 and concentrated. The crude residue was taken up in 100 mL dioxane, was treated with Pd2(dba)3 (0.399 g, 1.703 mmol), dicyclohexyl(2′,4′,6′-triisopropyl-[1,1′-biphenyl]-2-yl)phosphine (4.06 g, 8.52 mmol), bis(pinacolato)diboron (12.98 g, 51.1 mmol), and potassium phosphate (28.9 g, 136 mmol) and was heated to 120° C. overnight. LC/MS showed product, so the reaction mixture was diluted with heptane then filtered through a plug of diatomaceous earth. The filtrate was concentrated then purified directly by silica gel column chromatography (0-25% EtOAc/heptane) yielding 2-(4-cyclopropyl-2-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.68 g, 9.78 mmol, 28.7% yield). m/z (ESI) 297.3 (M+Na)+

Workup

  1. washwas washed with saturated NaHCO3 solution
  2. dry with materialThe organics were dried over MgSO4
  3. concentrationconcentrated
  4. filtrationthen filtered through a plug of diatomaceous earth
  5. concentrationThe filtrate was concentrated
  6. customthen purified directly by silica gel column chromatography (0-25% EtOAc/heptane)

Sources & evidence

ORD record
ord-f0af099227ca4c1da8a5be0f9dc44caa
Source dataset
uspto-grants-2015_04
Patent number
US09012443B2

Reaction notes

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