Binap, (A+-)- → HCID 58899093, compound

HRID 1181183Notes

Reaction equation

HRID 1181183 reaction equation
[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([NH2:10])=[CH:9][C:4]=2[CH2:3][CH2:2]1.Br[C:12]1[CH:13]=[CH:14][C:15]2[O:19][CH2:18][CH2:17][C:16]=2[CH:20]=1.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(C)([O-])C.[Na+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(C)C=CC=CC=1>[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([NH:10][C:12]3[CH:13]=[CH:14][C:15]4[O:19][CH2:18][CH2:17][C:16]=4[CH:20]=3)=[CH:9][C:4]=2[CH2:3][CH2:2]1

Participants

7

Reactant 4

HCID 634876Binap, (A+-)-HCID 27761595-Bromo-2,3-dihydro-1-benzofuranHCID 38411022,3-Dihydro-1-benzofuran-5-amineHCID 23676156Sodium t-butoxide

Product 1

HCID 58899093HCID 58899093, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

To a flask equipped with a magnetic stirrer, reflux condenser, and nitrogen inlet was added 2,3-dihydro-1-benzofuran-5-amine (4.53 grams, 33.3 mmoles, prepared as in Example 23 of U.S. Pat. No. 20040029932), 5-bromo-2,3-dihydrobenzofuran (6.63 grams, 32.9 mmoles), tris(dibenzylideneacetone)dipalladium (0) (0.61 grams, 0.67 mmoles), rac-2,2′-bis(diphenylphosphino)-1,1′-binapthyl (0.83 grams, 1.33 mmoles), sodium tert-butoxide (6.44 grams, 66.6 mmoles) and anhydrous toluene (60 mL). The contents of the flask were refluxed for three days; cooled to room temperature; and filtered through a pad of silica gel. The silica gel pad was then eluted with dichloromethane (200 mL). The combined organic layers were concentrated in vacuo to yield a dark yellow oil. The solid was chromatographed on silica gel, eluting with a hexane/ethyl acetate gradient. The resulting solid was recrystallized from ethanol to afford 1.8 grams of the desired product as a white solid. 1H NMR (CDCl3/D2O) δ 6.55-6.95 (m, 6H), 4.5 (t, 4H), 3.15 (t, 4H).

Workup

  1. customTo a flask equipped with a magnetic stirrer
  2. temperaturereflux condenser, and nitrogen inlet
  3. custom4.53 grams, 33.3 mmoles, prepared as in Example 23 of U.S
  4. temperatureThe contents of the flask were refluxed for three days
  5. filtrationand filtered through a pad of silica gel
  6. washThe silica gel pad was then eluted with dichloromethane (200 mL)
  7. concentrationThe combined organic layers were concentrated in vacuo
  8. customto yield a dark yellow oil
  9. customThe solid was chromatographed on silica gel
  10. washeluting with a hexane/ethyl acetate gradient
  11. customThe resulting solid was recrystallized from ethanol

Sources & evidence

ORD record
ord-27d159aced8f47cca1ba4ef9ab819f4b
Source dataset
uspto-grants-2007_10
Patent number
US07285518B2

Reaction notes

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