Potassium Carbonate → HCID 68668231, compound

HRID 1423355Notes

Reaction equation

HRID 1423355 reaction equation
FC(F)(F)S(O[C:7]1[CH2:12][CH2:11][CH2:10][CH2:9][C:8]=1[C:13]([O:15][CH2:16][CH3:17])=[O:14])(=O)=O.C(=O)([O-])[O-].[K+].[K+].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.B1(B2OC(C)(C)C(C)(C)O2)OC(C)(C)C(C)(C)O1.[Br:63][C:64]1[CH:69]=[CH:68][C:67](I)=[CH:66][C:65]=1[O:71][CH3:72]>O1CCOCC1.CCOC(C)=O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.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]>[Br:63][C:64]1[CH:69]=[CH:68][C:67]([C:7]2[CH2:12][CH2:11][CH2:10][CH2:9][C:8]=2[C:13]([O:15][CH2:16][CH3:17])=[O:14])=[CH:66][C:65]=1[O:71][CH3:72]

Participants

10

Reactant 5

HCID 11430Potassium Carbonate2×HCID 11776TriphenylphosphineHCID 394599Ethyl 2-[(trifluoromethanesulfonyl)oxy]cyclohex-1-ene-1-carboxylate2×HCID 2733548Bis(pinacolato)diboraneHCID 121872021-Bromo-4-iodo-2-methoxybenzene

Product 1

HCID 68668231HCID 68668231, compound

Reagents, catalysts & solvents 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of the product from Step 1, ethyl 2-{[(trifluoromethyl)sulfonyl]oxy}cyclohex-1-ene-1-carboxylate (6.65 g, 22.0 mmol) in dioxane (125 mL) was added potassium carbonate (4.56 g, 33.0 mmol), PPh3 (0.346 g, 1.32 mmol), bis(pinacolato)diboron (6.15 g, 24.20 mmol), and PdCl2(PPh3)2 (0.463 g, 0.66 mmol). The mixture was then heated to 80° C. overnight. This solution was then cooled to r.t. and added to a mixture of 1-bromo-4-iodo-2-methoxybenzene (6.86 g, 21.92 mmol), PdCl2(dppf) (0.481 g, 0.657 mmol), potassium carbonate (9.09 g, 65.7 mmol). This mixture was then heated to 80° C. overnight. The mixture was then cooled to r.t., diluted with EtOAc (300 mL) and washed with brine and aqueous KHSO4. The organic layer was then dried over Na2SO4 and the solvent was removed in vacuo. The crude material was then purified on silica (100% DCM) to give impure product which was repurified on silica (gradient elution, 5-20% EtOAc/hexanes) to give the title compound.

Workup

  1. temperatureThis solution was then cooled to r.t.
  2. temperatureThis mixture was then heated to 80° C. overnight
  3. temperatureThe mixture was then cooled to r.t.
  4. washwashed with brine and aqueous KHSO4
  5. dry with materialThe organic layer was then dried over Na2SO4
  6. customthe solvent was removed in vacuo
  7. customThe crude material was then purified on silica (100% DCM)
  8. customto give impure product which
  9. customwas repurified on silica (gradient elution, 5-20% EtOAc/hexanes)

Sources & evidence

ORD record
ord-b05ceb0601944c808c8a5c88956cd0c5
Source dataset
uspto-grants-2015_01
Patent number
US08927569B2

Reaction notes

Loading…