1-Iodo-4-nitrobenzene → Methyl 2-(4-(4'-nitrobiphenyl-4-yl)-2-oxabicyclo[2.2.2]octan-1-yl)acetate

HRID 881724Notes

Reaction equation

HRID 881724 reaction equation
CC1(C)C(C)(C)OB([C:9]2[CH:14]=[CH:13][C:12]([C:15]34[CH2:22][CH2:21][C:18]([CH2:23][C:24]([O:26][CH3:27])=[O:25])([CH2:19][CH2:20]3)[O:17][CH2:16]4)=[CH:11][CH:10]=2)O1.I[C:30]1[CH:35]=[CH:34][C:33]([N+:36]([O-:38])=[O:37])=[CH:32][CH:31]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+]>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].ClCCl.C(COC)OC>[N+:36]([C:33]1[CH:34]=[CH:35][C:30]([C:9]2[CH:10]=[CH:11][C:12]([C:15]34[CH2:20][CH2:19][C:18]([CH2:23][C:24]([O:26][CH3:27])=[O:25])([CH2:21][CH2:22]3)[O:17][CH2:16]4)=[CH:13][CH:14]=2)=[CH:31][CH:32]=1)([O-:38])=[O:37]

Participants

6

Reactant 3

HCID 124951-Iodo-4-nitrobenzeneHCID 62657Potassium Phosphate, TribasicHCID 86700826Methyl 2-(4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-2-oxabicyclo[2.2.2]octan-1-yl)acetate

Product 1

HCID 86700831Methyl 2-(4-(4'-nitrobiphenyl-4-yl)-2-oxabicyclo[2.2.2]octan-1-yl)acetateYield 79%

Reagents, catalysts & solvents 2

HCID 178418807HCID 178418807, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

To a round bottom flask containing methyl 2-(4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-2-oxabicyclo[2.2.2]octan-1-yl)acetate (800 m g, 2.07 mmol), 1-iodo-4-nitrobenzene (619 mg, 2.49 mmol) and K3PO4 (528 mg, 2.49 mmol) was added dimethoxyethane (24 ml) at room temperature. The mixture was stirred at room temperature and degassed after the addition of EtOH (8 ml) and water (3.2 ml). PdCl2(dppf) dichloromethane adduct (85 mg, 0.10 mmol) was added and the mixture was heated to 8° C. in an oil bath for overnight. The reaction mixture was then concentrated to dryness and taken up in DCM. The slurry was dried over sodium sulfate and filtered through a pad of celite. The filtrate was concentrated and purified by column chromatography affording the title compound as off-white solid (624 mg, 79% yield). LC/MS, ESI-MS(+): 382.4, RT: 1.49 (Condition E).

Workup

  1. customdegassed
  2. additionafter the addition of EtOH (8 ml) and water (3.2 ml)
  3. temperaturethe mixture was heated to 8° C. in an oil bath for overnight
  4. concentrationThe reaction mixture was then concentrated to dryness
  5. dry with materialThe slurry was dried over sodium sulfate
  6. filtrationfiltered through a pad of celite
  7. concentrationThe filtrate was concentrated
  8. custompurified by column chromatography

Sources & evidence

ORD record
ord-58a984f7534f480da937a98253996e92
Source dataset
uspto-grants-2015_03
Patent number
US08993619B2

Reaction notes

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