Diethyl Ether → (1s,2s)-2-(4-Chlorophenoxy)-1,2,-dihydro-naphthalen-1-ol

HRID 1060712Notes

Reaction equation

HRID 1060712 reaction equation
[CH2:1]1[CH2:5][O:4][CH2:3][CH2:2]1.[Cl:6][C:7]1[CH:12]=[CH:11][C:10]([OH:13])=[CH:9][CH:8]=1.C(O[CH2:17][CH3:18])C>>[Cl:6][C:7]1[CH:12]=[CH:11][C:10]([O:13][C@H:18]2[CH:17]=[CH:5][C:1]3[C:2](=[CH:5][CH:1]=[CH:2][CH:3]=3)[C@@H:3]2[OH:4])=[CH:9][CH:8]=1

Participants

4

Reactant 3

HCID 3283Diethyl EtherHCID 46844-ChlorophenolHCID 8028Tetrahydrofuran

Product 1

HCID 9903605(1s,2s)-2-(4-Chlorophenoxy)-1,2,-dihydro-naphthalen-1-olYield 89%

Conditions

Temperature
80 °C

Procedure

To a flame dried round-bottomed flask, [Rh(COD)Cl]2 (1.7 mg, 0.0035 mmol), (S)-(R)-PPF-PtBu2 (3.8 mg, 0.0069 mmol) and 1 (100 mg, 0.694 mmol) were added followed by addition of THF (2.5 mL) and 4-chlorophenol (446 mg, 3.47 mmol). The mixture was heated at 80° C. for 6 hours, then poured into diethyl ether and extracted 3 times with 10% aqueous sodium hydroxide solution. The aqueous extracts were combined and back-extracted three times with diethyl ether. The combined ether extracts were washed with brine and dried with anhydrous sodium sulfate. The solvents were removed in vacuo, yielding a solid which was purified by flash chromatography on silica gel (5% ethyl acetate in hexanes) giving a white crystalline solid 8 (169 mg, 89%). The ee was determined to be 92% by formation of Mosher's ester. Rf=0.47 on silica (20% ethyl acetate in hexanes); mp 125-125.5° C. (Et2O); [α]25D+150° (c=10.6, CHCl3). IR (KBr, cm−1) 3302 (br), 3064 (w), 2874 (w), 1590 (m), 1489 (s), 1362 (w), 1230 (s), 1052 (m), 890 (w), 846 (m), 778 (s), 663 (m); 1H NMR (400 MHz, CDCl3): δ7.65-7.64 (1H, m), 7.33-7.26 (4H, m), 7.16-7.13 (1H, m), 6.91(1H, ddd, J=2.0, 2.0, 8.9 Hz), 6.55 (1H, dd, J=1.8, 9.9 Hz), 5.99 (1H, dd, J=2.2, 9.9 Hz), 5.19 (1H, dd, J=3.8, 10.0 Hz), 5.07 (1H, ddd, J=2.0, 2.0, 10.1 Hz), 2.56 (1H, d, J=4.0 Hz); 13C NMR (400 MHz, CDCl3): δ155.8, 135.2, 131.7, 129.5, 129.3, 128.2, 128.1, 126.5, 126.2, 125.3, 125.2, 116.9, 79.2, 72.1. HRMS calcd for (M-H2O)+ (C16H11OCl): 254.0498. Found: 254.0499.

Workup

  1. extractionextracted 3 times with 10% aqueous sodium hydroxide solution
  2. extractionback-extracted three times with diethyl ether
  3. washThe combined ether extracts were washed with brine
  4. dry with materialdried with anhydrous sodium sulfate
  5. customThe solvents were removed in vacuo
  6. customyielding a solid which
  7. customwas purified by flash chromatography on silica gel (5% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-d57c5d3bda2749ef918cff84ead4a1a6
Source dataset
uspto-grants-2003_02
Patent number
US06525068B1

Reaction notes

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