Sodium Carbonate → 9-[3-(1-Adamantyl)-4-benzylphenyl]-6-(2-carboxyphenyl)xanthen-3-one

HRID 1826611Notes

Reaction equation

HRID 1826611 reaction equation
FC(F)(F)S(O[C:7]1[C:8]2[C:13]([O:14][C:15]3[C:20]=1[CH:19]=[CH:18][C:17](=[O:21])[CH:16]=3)=[CH:12][C:11]([C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=1[C:28]([OH:30])=[O:29])=[CH:10][CH:9]=2)(=O)=O.[C:33]12(C3C=C(B(O)O)C=CC=3OCC3C=CC=CC=3)[CH2:42][CH:37]3[CH2:38][CH:39]([CH2:41][CH:35]([CH2:36]3)[CH2:34]1)[CH2:40]2.[Li+].[Cl-].C([O-])([O-])=O.[Na+].[Na+]>COCCOC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCOC(C)=O.CCCCCC>[C:33]12([C:15]3[CH:16]=[C:17]([C:7]4[C:8]5[C:13]([O:14][C:15]6[C:20]=4[CH:19]=[CH:18][C:17](=[O:21])[CH:16]=6)=[CH:12][C:11]([C:22]4[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=4[C:28]([OH:30])=[O:29])=[CH:10][CH:9]=5)[CH:18]=[CH:19][C:20]=3[CH2:7][C:8]3[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=3)[CH2:40][CH:39]3[CH2:38][CH:37]([CH2:36][CH:35]([CH2:41]3)[CH2:34]1)[CH2:42]2

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 433294Lithium ChlorideHCID 12134904[3-(Adamantan-1-yl)-4-(benzyloxy)phenyl]boronic acidHCID 221347779-(Trifluoromethane-sulfonyloxy)-6-(2-carboxyphenyl)xanthen-3-one

Product 1

HCID 221347979-[3-(1-Adamantyl)-4-benzylphenyl]-6-(2-carboxyphenyl)xanthen-3-one

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

To a stirred suspension of 1.00 g (2.15 mmol) of 9-(trifluoromethane-sulfonyloxy)-6-(2-carboxyphenyl)xanthen-3-one, 0.80 g (2.20 mmol) of 3-(1-adamantyl)-4-benzyloxyphenylboronic acid [1H NMR (300 MHz, CDCl3) δ 1.77, 2.26 (2 s, 12, AdCH2), 2.07 (s, 3, AdCH), 5.21 (s, 2, CH2), 7.06 (d, J=8.2 Hz, 1, ArH), 7.3–7.5 (m, 5, ArH), 8.03 (d, J=7.8 Hz, 1, ArH), 8.19 ppm (s, 1, ArH)], 0.32 g (0.28 mmol) of Pd[P(C6H5)3]4 and 0.26 g (6.1 mmol) of LiCl in 20 ml of DME was added under Ar 3 ml of 2.0 M aq. Na2CO3. The reaction mixture was heated at reflux (80–85° C.) overnight, at which time the reaction was complete. The mixture was extracted with EtOAc. The extract was washed with brine and water, dried (MgSO4), filtered, and concentrated. Flash column chromatography (10% EtOAc/hexane) yielded a pale red (0.60 g, 44%): Rf0.45 (40% EtOAc/hexane); 1H NMR (400 MHz, CDCl3) δ 1.74, 2.19 (2 s, 12, AdCH2), 2.06 (s, 3, AdCH), 5.17 (s, 2, CH2), 6.55 (dd, J=8.0, 2.0 Hz, 1, ArH), 6.68 (d, J=8.0 Hz, 1, ArH), 6.8–7.7 (m, 16, ArH), 8.05 ppm (d, J=8.0 Hz, 1, ArH).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux (80–85° C.) overnight
  3. extractionThe mixture was extracted with EtOAc
  4. washThe extract was washed with brine and water
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customFlash column chromatography (10% EtOAc/hexane) yielded a pale red (0.60 g, 44%)

Sources & evidence

ORD record
ord-160c8ae2566a47a9a6676277914cabeb
Source dataset
uspto-grants-2006_05
Patent number
US07053071B2

Reaction notes

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