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

HRID 1837678Notes

Reaction equation

HRID 1837678 reaction equation
[CH2:1]1[CH2:5][O:4][CH2:3][CH2:2]1.[C:6]([C:8]1[CH:13]=[CH:12][C:11]([OH:14])=[CH:10][CH:9]=1)#[N:7].C(O[CH2:18][CH3:19])C>>[C:6]([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)#[N:7]

Participants

4

Reactant 3

HCID 3283Diethyl EtherHCID 8028TetrahydrofuranHCID 130194-Cyanophenol

Product 1

HCID 9816715(1s,2s)-2-(4-Cyanophenoxy)-1,2,-dihydro-naphthalen-1-olYield 88%

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-cyanophenol (413 mg, 3.47 mmol). The mixture was heated at 80° C. for 5 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 (30% ethyl acetate in hexanes) giving a white crystalline solid 4 (160 mg, 88%). The ee was determined to be 97% by HPLC analysis on a CHIRALCEL OD column, λ=256 nm. Retention times in 3% isopropanol in hexanes were 35.3 min and 37.7 min (major). Fr=0.40 on silica (30% ethyl acetate in hexanes); mp 140-141° C. (Et2O); [α]25D=+182.3° (c=11.2, CHCl3) IR (KBr, cm−1) 3303 (b) 3050 (w) 2210 (m) 1598 (s) 1503 (s) 1238 (s) 1025 (m) 859 (m) 778 (m); 1H NMR (400 MHz, CDCl3): δ 7.62-7.57 (3H, m), 7.33-7.27 (3H, m), 7.14-7.12 (1H, m), 6.56 (1H, dd, J=1.4, 9.7 Hz), 5.93 (1H, dd, J=1.4, 9.7 Hz), 5.20-5.13 (2H, m), 2.25 (1H, s). 13C NMR (400 MHz, CDCl3): δ 160.8, 135.0, 134.2, 131.5, 130.0, 128.5, 128.3, 126.7, 125.4, 124.4, 119.0, 116.2, 104.6, 79.2, 72.0. HRMS calcd for (M-H2O)+ (C17H11ON): 245.0841. Found: 245.0845.

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 (30% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-0106dba5c9eb497b8ffb1cb9d4fd54fc
Source dataset
uspto-grants-2004_08
Patent number
US06784210B2

Reaction notes

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