Diethyl Ether → HCID 9816835, compound

HRID 28799Notes

Reaction equation

HRID 28799 reaction equation
[CH2:1]1[CH2:5][O:4][CH2:3][CH2:2]1.[CH3:6][O:7][C:8]1[CH:13]=[CH:12][C:11]([OH:14])=[CH:10][CH:9]=1.C(O[CH2:18][CH3:19])C>>[CH3:6][O:7][C:8]1[CH:13]=[CH:12][C:11]([O:14][C@H:19]2[CH:18]=[CH:5][C:1]3[C:2](=[CH:5][CH:1]=[CH:2][CH:3]=3)[C@@H:3]2[OH:4])=[CH:10][CH:9]=1

Participants

4

Reactant 3

HCID 3283Diethyl EtherHCID 8028TetrahydrofuranHCID 90154-Methoxyphenol

Product 1

HCID 9816835HCID 9816835, compound

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-PtBu, (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-methoxyphenol (431 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 vactio, yielding a solid which was purified by flash chromatography on silica gel (10% ethyl acetate in hexanes) as a white crystalline solid 12 (159 mg, 85%). The ee was determined to be 95% by HPLC analysis on a CHIRALCEL OD column, λ=256 nm. Retention times in 4% isopropanol in hexanes were 22.1 min (major) and 25.9 min. Rf=0.33 on silica (20% ethyl acetate in hexanes); mp 91-92° C. (Et2O); [α]25D=+129° (c=9.9, CHCl3); IR (KBr, cm−1) 3349 (br), 3050 (w), 2822 (w), 1508 (s), 1233 (s), 1046 (m), 825 (m), 751 (m), 695 (w); 1H NMR (400 MHz, CDCl3): δ 7.66-7.64 (1H, m), 7.30-7.27 (2H, m), 7.12-7.10 (1H, m), 6.91 (2H, ddd, J=2.3, 2.3, 9.1 Hz), 6.84 (2H, ddd, J=2.4, 2.4, 9.2 Hz), 6.49 (1H, dd, J=2.0, 9.9 Hz), 6.02 (1H, dd, J=2.4, 9.9 Hz), 5.17 (1H, dd, J=3.3, 10.1 Hz), 5.02 (1H, ddd, J=2.0, 2.0, 10.3 Hz), 3.77 (3H, s), 3.12 (1H, d, J=3.4 Hz). 13C NMR (400 MHz, CDCl3): δ 154.3, 151.2, 135.5, 131.9, 128.7, 128.1, 127.9, 126.4, 126.3, 125.2, 117.2, 114.8, 80.0, 72.4, 55.7. HRMS calcd for (M+) (C17H14O2): 250.0994. Found: 250.1006.

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 vactio
  6. customyielding a solid which
  7. customwas purified by flash chromatography on silica gel (10% ethyl acetate in hexanes) as a white crystalline solid 12 (159 mg, 85%)
  8. custom(major) and 25.9 min

Sources & evidence

ORD record
ord-eaa57c5870354fbe9f623a527e6687d0
Source dataset
uspto-grants-2008_09
Patent number
US07420003B2

Reaction notes

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