Dichloromethane → Dimethyl 2,3-biphenyldicarboxylate

HRID 593692Notes

Reaction equation

HRID 593692 reaction equation
I[C:2]1[CH:11]=[CH:10][CH:9]=[C:4]([C:5]([O:7][CH3:8])=[O:6])[C:3]=1[C:12]([O:14][CH3:15])=[O:13].[C:16]1(B(O)O)[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.C([O-])([O-])=O.[K+].[K+].C(Cl)Cl>O1CCOCC1.O.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:2]1([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[CH:11]=[CH:10][CH:9]=[C:4]([C:5]([O:7][CH3:8])=[O:6])[C:3]=1[C:12]([O:14][CH3:15])=[O:13]

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 66827Phenylboronic AcidHCID 2326127Dimethyl 3-iodophthalate

Product 1

HCID 22341661Dimethyl 2,3-biphenyldicarboxylateYield 77.1%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A solution of dimethyl 3-iodophthalate (WO 2008/115516) (1.00 g, 3.12 mmol), phenylboronic acid (0.571 g, 4.69 mmol), K2CO3 (0.880 g, 9.30 mmol) in 1,4-dioxane (15 mL) and water (4 mL) was purged with nitrogen for 30 min. Pd(dppf)Cl2:DCM (0.219 g, 0.312 mmol) was added and the reaction mixture was heated at 100° C. for 12 h. The reaction mixture was filtered through a pad of CELITE® and the pad was washed with water (50 mL). The filtrate was extracted with EtOAc (2×100 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The resulting residue was purified by combiflash (REDISEP®, silica gel, 12 g, 20% EtOAc/hexanes) to obtain dimethyl [1,1′-biphenyl]-2,3-dicarboxylate (0.65 g, 77.0%) as an off-white solid. LCMS (Condition 11): retention time 0.96 min, [M-MeOH+1]=239.3. 1H NMR (400 MHz, DMSO-d6) δ 3.59 (s, 3 H), 3.85 (s, 3 H), 7.33-7.49 (m, 5 H), 7.68-7.70 (m, 2 H), 7.95-8.00 (m, 1 H).

Workup

  1. filtrationThe reaction mixture was filtered through a pad of CELITE®
  2. washthe pad was washed with water (50 mL)
  3. extractionThe filtrate was extracted with EtOAc (2×100 mL)
  4. dry with materialThe combined organic extracts were dried over anhydrous Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe resulting residue was purified by combiflash (REDISEP®, silica gel, 12 g, 20% EtOAc/hexanes)

Sources & evidence

ORD record
ord-ec8c7df8ae8748b3ae8ac33d36f217de
Source dataset
uspto-grants-2016_01
Patent number
US09242966B2

Reaction notes

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