Cesium carbonate → HCID 68109805, compound

HRID 2179392Notes

Reaction equation

HRID 2179392 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH2:22][CH:23]([OH:25])[CH3:24])[C:5]2[O:14][C:13]3[CH2:12][CH2:11][N:10]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:9][C:8]=3[C:6]=2[CH:7]=1.[C:26]1([S:32]([O-:34])=[O:33])[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=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>[OH:25][CH:23]([CH3:24])[CH2:22][C:4]1[C:5]2[O:14][C:13]3[CH2:12][CH2:11][N:10]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH2:9][C:8]=3[C:6]=2[CH:7]=[C:2]([S:32]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)(=[O:34])=[O:33])[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 68108948HCID 68108948, compound

Product 1

HCID 68109805HCID 68109805, compoundYield 44%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of tert-butyl 8-bromo-6-(2-hydroxypropyl)-3,4-dihydrobenzofuro[3,2-c]pyridine-2(1H)-carboxylate (110 mg, 0.27 mmol), sodium benzenesulfinate (53 mg, 0.32 mmol), di-palladium-tris(dibenzylideneacetone) (24 mg, 0.03 mmol), cesium carbonate (131 mg, 0.40 mmol) and xantphos (31 mg, 0.06 mmol) was suspended in anhydrous toluene (8 mL). The flask was purged with argon, sealed, and heated to 120° C. for 14 h. The reaction mixture was cooled, diluted with dichloromethane, and filtered through a celite bed. The filtrate was concentrated in vacuo to give the crude product which was purified by flash column chromatography (SiO2, 4:1 hexanes/ethyl acetate) to give tert-butyl 6-(2-hydroxypropyl)-8-(phenylsulfonyl)-3,4-dihydrobenzofuro[3,2-c]pyridine-2(1H)-carboxylate (50 mg, 44%) as a white solid: 1H NMR (CDCl3, 300 MHz) δ 8.00-7.92 (m, 3H), 7.71 (s, 1H), 7.58-7.45 (m, 3H), 4.56 (br s, 2H), 4.26-4.17 (m, 1H), 3.83 (s, 2H), 3.04 (t, J=3.9 Hz, 2H), 2.86 (br s, 2H), 1.51 (s, 9H), 1.25 (d, J=4.8 Hz, 3H).

Workup

  1. customThe flask was purged with argon
  2. customsealed
  3. temperatureThe reaction mixture was cooled
  4. additiondiluted with dichloromethane
  5. filtrationfiltered through a celite bed
  6. concentrationThe filtrate was concentrated in vacuo
  7. customto give the crude product which
  8. customwas purified by flash column chromatography (SiO2, 4:1 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-82cfa1189dd6451cbf466414101a7d32
Source dataset
uspto-grants-2015_06
Patent number
US09067949B2

Reaction notes

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