Ethyl cinnamyl carbonate → 1-Phenyl-1-phenoxy-2-propene

HRID 14440Notes

Reaction equation

HRID 14440 reaction equation
CC1(C)C(C=C[C:13]2[CH2:39][CH2:38][CH2:37]/[C:15](=[CH:16]/[CH:17]=[C:18]3/C(C)(C)C4C(N/3CCCCS(O)(=O)=O)=CC=CC=4)/[C:14]=2[O:40][C:41]2[CH:46]=[CH:45][C:44](OCCCCNCC3OC(O)C(N)C(O)C3O)=[CH:43][CH:42]=2)=[N+](CCCCS([O-])(=O)=O)C2C1=CC=CC=2.[O-]C1C=CC=CC=1.[Na+].C(=O)(OCC=CC1C=CC=CC=1)OCC>C1COCC1.[Cl-].[Na+].O>[C:15]1([CH:14]([O:40][C:41]2[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=2)[CH:13]=[CH2:39])[CH:16]=[CH:17][CH:18]=[CH:38][CH:37]=1

Participants

6

Reactant 3

HCID 232463Ethyl cinnamyl carbonateHCID 4445035Phenolate SodiumHCID 178424610HCID 178424610, compound

Product 1

HCID 117359621-Phenyl-1-phenoxy-2-propeneYield 75%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

[(COD)Ir(κ2-L1)(L1)] (Ir-2) (13.8 mg, 0.0100 mmol), [(COD)IrCl]2 (3.4 mg, 0.0050 mmol) and sodium phenoxide (232 mg, 2.00 mmol) were dissolved in 1.0 mL of THF. Ethyl cinnamyl carbonate (192 mg, 0.930 mmol) was added to the reaction mixture by syringe. After being stirred at room temperature for 2 h, the reaction mixture was poured into brine, extracted with ether, dried, filtered, and concentrated. 1H NMR analysis of the mixture indicated that the ratio of branched to linear regioisomers was 95/5. The residue was purified by flash chromatography on silica gel (1% Et2O/Hexanes) to afford 157 mg (75%) of 1-phenyl-1-phenoxy-2-propene as a viscous oil. [Rf 0.85 (5% Et2O/Hexanes)] HPLC analysis indicated an enantiomeric excess of 94% [Chiralcel® OJ-H column, eluting with 99.75/0.25 hexane/i-PrOH, 0.6 mL/min, 220 nm; major enantiomer TR, 45.4, minor enantiomer TR 55.3 min]; [α]D20=+8.9 (c 1.4, CHCl3); 1H NMR (500.13 MHz, CDCl3) δ 7.48-7.27 (m, 8H), 7.01-6.96 (m, 2H), 6.15 (ddd, J=17.2, 10.4, 5.9 Hz, 1H), 5.70 (d, J=5.9 Hz, 1H), 5.41 (d, J=17.2 Hz, 1H), 5.31 (d, J=10.4 Hz, 1H). 13C NMR (125.7 MHz, CDCl3) δ 157.9 (C), 140.1 (C), 137.9 (CH), 129.3 (CH), 128.6 (CH), 127.8 (CH), 126.6 (CH), 121.0 (CH), 116.5 (CH2), 116.2 (CH), 80.8 (CH).

Workup

  1. extractionextracted with ether
  2. customdried
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe residue was purified by flash chromatography on silica gel (1% Et2O/Hexanes)

Sources & evidence

ORD record
ord-787d893ae1a94fe2867eace2a9f53ac9
Source dataset
uspto-grants-2010_06
Patent number
US07732365B2

Reaction notes

Loading…