Cesium carbonate → HCID 68108804, compound

HRID 2179442Notes

Reaction equation

HRID 2179442 reaction equation
Br[C:2]1[CH:3]=[C:4]([Cl:16])[C:5]2[O:9][C:8]3[CH2:10][CH2:11][CH:12]([OH:14])[CH2:13][C:7]=3[C:6]=2[CH:15]=1.[C:17]1([S:23]([O-:25])=[O:24])[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.[Na+].C(=O)([O-])[O-].[Cs+].[Cs+].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>C1(C)C=CC=CC=1>[Cl:16][C:4]1[C:5]2[O:9][C:8]3[CH2:10][CH2:11][CH:12]([OH:14])[CH2:13][C:7]=3[C:6]=2[CH:15]=[C:2]([S:23]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)(=[O:25])=[O:24])[CH:3]=1

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 2723840Benzenesulfinic acid, sodium saltHCID 68108476HCID 68108476, compound

Product 1

HCID 68108804HCID 68108804, compoundYield 28.3%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of the product of step B (120 mg, 0.39 mmol), sodium benzenesulfinate (77 mg, 0.47 mmol), di-palladium-tris(dibenzylideneacetone) (36 mg, 0.04 mmol), cesium carbonate (190 mg, 0.58 mmol) and xantphos (45 mg, 0.08 mmol) was suspended in anhydrous toluene (5.0 mL). The reaction flask was purged with argon and heated to 110° C. for 1 h. After cooling to ambient temperature, the reaction mixture was diluted with dichloromethane and filtered through a celite bed. The filtrate was concentrated in vacuo and the residue purified by flash column chromatography (SiO2, 9:1 hexanes/ethyl acetate) and triturated with MTBE to give 6-chloro-8-(phenylsulfonyl)-1,2,3,4-tetrahydrodibenzo[b,d]furan-2-ol (40 mg, 27%, AUC HPLC 97.1%) as a white solid: mp 236-240° C.; 1H NMR (DMSO-d6, 400 MHz) δ 8.15 (d, J=1.6 Hz, 1H), 8.05-8.01 (m, 2H), 7.89 (d, J=1.6 Hz, 1H), 7.71-7.66 (m, 1H), 7.64-7.59 (m, 2H), 4.92 (d, J=4.0 Hz, 1H), 4.11-4.04 (m, 1H), 2.94-2.76 (m, 3H), 2.60-2.52 (m, 1H), 2.00-1.87 (m, 2H); ESI MS m/z 363 [M+H]+.

Workup

  1. customThe reaction flask was purged with argon
  2. temperatureAfter cooling to ambient temperature
  3. additionthe reaction mixture was diluted with dichloromethane
  4. filtrationfiltered through a celite bed
  5. concentrationThe filtrate was concentrated in vacuo
  6. customthe residue purified by flash column chromatography (SiO2, 9:1 hexanes/ethyl acetate)
  7. customtriturated with MTBE

Sources & evidence

ORD record
ord-8622451075f843bd9c0a15c53604f98d
Source dataset
uspto-grants-2015_06
Patent number
US09067949B2

Reaction notes

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