Formic Acid → 1-Indanol

HRID 1454055Notes

Reaction equation

HRID 1454055 reaction equation
C(O)=O.[C:4]1(=[O:13])[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[CH2:6][CH2:5]1.C(N(CC)CC)C.C(=O)([O-])O.[Na+]>ClCCl>[CH:4]1([OH:13])[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[CH2:6][CH2:5]1

Participants

6

Reactant 4

HCID 284Formic Acid2×HCID 67351-IndanoneHCID 8471TriethylamineHCID 516892Sodium Bicarbonate

Product 1

HCID 228191-Indanol

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
30 °C

Procedure

Formic acid (7.2 mL, 190.7 mmol) was added dropwise to a stirred solution of 1-indanone (5.09 g, 38.5 mmol), (S,S)-TsDPEN Ru (p-cymene) Cl (231 mg, 0.36 mmol) and triethylamine (26 mL, 186.5 mmol) in dichloromethane (50 mL) at 30° C. (internal) under a nitrogen atmosphere over a period of 30 minutes. The internal temperature reached 35° C. during the addition. After stirring for 19 hours at 30° C., 1H NMR analysis indicated a conversion of 80%. Additional (S,S)-TsDPEN Ru (p-cymene)Cl (47 mg, 0.07 mmol) was added to the reaction mixture followed by formic acid (3 mL, 79.5 mmol) dropwise over 30 minutes. After stirring for 21 hours at 35° C. (internal), 1H NMR analysis indicated complete conversion. The reaction was allowed to cool to room temperature before saturated aqueous sodium hydrogen carbonate solution (100 mL) was added. The two layers were separated then the aqueous layer was further extracted with dichloromethane (80 mL). The combined organic layers were washed with water (80 mL), dried (MgSO4), filtered and concentrated under reduced pressure. The crude material was purified by passage trough a pad of silica using methyl tert-butyl ether as eluant to afford the S-enantiomer of the title compound as a red solid. (5.06 g, 98%). 1H NMR (400 MHz, d6-DMSO) δ ppm 7.37-7.34 (1H, m, Ar), 7.26-7.19 (3H, m, Ar), 5.23 (1H, d, J6, OH), 5.06 (1H, dt, J6 and 6, CH), 2.97-2.90 (1H, m, CHH), 2.77-2.69 (1H, m, CHH), 2.39-2.31 (1H, m, CHH) and 1.84-1.75 (1H, m, CHH). Analysis of this material by chiral GC indicated it to be 98% e.e.

Workup

  1. additionThe internal temperature reached 35° C. during the addition
  2. stirringAfter stirring for 21 hours at 35° C. (internal), 1H NMR analysis
  3. additionwas added
  4. customThe two layers were separated
  5. extractionthe aqueous layer was further extracted with dichloromethane (80 mL)
  6. washThe combined organic layers were washed with water (80 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe crude material was purified by passage trough a pad of silica

Sources & evidence

ORD record
ord-95109d5fa2a24e818dc1cab1a36f300c
Source dataset
uspto-grants-2009_01
Patent number
US07476757B2

Reaction notes

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