Tetrahydrofuran → HCID 15302813, compound

HRID 984719Notes

Reaction equation

HRID 984719 reaction equation
C[C:2]([O-:5])(C)C.[Na+].C1C=CC(P([C:20]2[C:29]([C:30]3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=[C:36]4[C:31]=3[CH:32]=[CH:33][CH:34]=[CH:35]4)=[C:28]3[C:23]([CH:24]=[CH:25][CH:26]=[CH:27]3)=CC=2)C2C=CC=CC=2)=CC=1.C1C[O:56]CC1>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]>[CH3:2][O:5][C:24]1[CH:23]=[C:28]([CH:29]([CH3:20])[C:30]([C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)=[O:56])[CH:27]=[CH:26][CH:25]=1

Participants

5

Reactant 3

HCID 8028TetrahydrofuranHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxide

Product 1

HCID 15302813HCID 15302813, compoundYield 89%

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Procedure

An oven-dried Schlenk tube containing a stir bar was charged with Pd2(dba)3 (6.9 mg, 0.0075 mmol, 1.5 mol %), ligand (0.018 mmol, 3.6 mol %), and NaOt-Bu (65 mg, 0.65 mmol). The Schlenk tube was evacuated and back filled with argon. THF (2 mL) was added followed by aryl halide (0.5 mmol), ketone (0.6 mmol or 1.0 mmol), and additional THF (1 !mL). The resulting red mixture was heated under argon at 70° C. until the starting halide had been consumed as judged by GC analysis. The Schlenk tube was cooled to room temperature, and diethyl ether (25 mL) and H2O (25 mL) were added. The aqueous layer was separated and extracted with diethyl ether (25 mL). The organic layers were combined, washed with brine (40 mL), dried over MgSO4, filtered, and concentrated. The crude product was then purified by flash chromatography on silica gel. Using 0.6 mmol of ketone and BINAP gave 107 mg (89% yield) of a colorless oil. 1H NMR (CDCl3, 250 MHz) δ 7.92-7.96 (m, 2H), 7.31-7.44 (m, 3H), 7.19 (t, J=7.0 Hz, 1H), 6.82-6.88 (m 2H), 6.72 (dd, J=8.3, 2.3 Hz, H), 4.64 (q, J=6.8 Hz, 1H), 3.73 (s, 3H), 1.52 (d, J=6.8 Hz, 3H); 13C NMR (CDCl3, 250 MHz) 5200.1, 150.0, 143.0, 136.6, 132.7, 129.9, 128.7, 128.4, 120.2, 113.5, 112.2, 55.1, 47.9, 19.3; IR (neat, cm−1) 2975, 2932, 1682, 1597, 1583. Anal Calcd for C16H602: C, 79.97; H, 6.71. Found: C, 79.89; H, 6.62.

Workup

  1. additionAn oven-dried Schlenk tube containing a stir bar
  2. customThe Schlenk tube was evacuated
  3. additionback filled with argon
  4. additionTHF (2 mL) was added
  5. customhad been consumed
  6. additiondiethyl ether (25 mL) and H2O (25 mL) were added
  7. customThe aqueous layer was separated
  8. extractionextracted with diethyl ether (25 mL)
  9. washwashed with brine (40 mL)
  10. dry with materialdried over MgSO4
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customThe crude product was then purified by flash chromatography on silica gel

Sources & evidence

ORD record
ord-14b7c38df02b4ceb92b88cbf2434a6ca
Source dataset
uspto-grants-2005_03
Patent number
US06867310B1

Reaction notes

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