Formic Acid → ((S)-5-Hydroxy-5,6,7,8-tetrahydro-naphthalen-1-yloxy)-acetic acid tert-butyl ester

HRID 1696877Notes

Reaction equation

HRID 1696877 reaction equation
CC1C=CC(S(N[C@H]([C@@H](N)C2C=CC=CC=2)C2C=CC=CC=2)(=O)=O)=CC=1.C(O)=O.C(N(CC)CC)C.[C:37]([O:41][C:42](=[O:56])[CH2:43][O:44][C:45]1[C:54]2[CH2:53][CH2:52][CH2:51][C:50](=[O:55])[C:49]=2[CH:48]=[CH:47][CH:46]=1)([CH3:40])([CH3:39])[CH3:38]>O>[C:37]([O:41][C:42](=[O:56])[CH2:43][O:44][C:45]1[C:54]2[CH2:53][CH2:52][CH2:51][C@H:50]([OH:55])[C:49]=2[CH:48]=[CH:47][CH:46]=1)([CH3:40])([CH3:38])[CH3:39]

Participants

6

Reactant 4

HCID 284Formic AcidHCID 8471TriethylamineHCID 6612782(1S,2S)-(+)-N-p-Tosyl-1,2-diphenylethylenediamineHCID 59192613Tert-butyl 2-((5-oxo-5,6,7,8-tetrahydronaphthalen-1-yl)oxy)acetate

Product 1

HCID 59192543((S)-5-Hydroxy-5,6,7,8-tetrahydro-naphthalen-1-yloxy)-acetic acid tert-butyl ester

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a flask containing 124 mg (0.203 mmol) of di-mu-chlorobis[(p-cymene)chlororuthenium(II) ([RuCl2(C10H14)]2, Strem Chemicals, Inc., CAS No. 52462-29-0) and 153 mg (0.416 mmol) of (1S,2S)-(+)-N-p-tosyl-1,2-diphenylethylenediamine (Aldrich, CAS No. 167316-27-0) was added 50 mL of a pre-formed mixture of formic acid and triethylamine (in 5:2 molar ratio), and the resulting mixture was stirred at room temperature for 45 minutes (gas evolution was observed). Then 10 g (36.19 mmol) of (5-oxo-5,6,7,8-tetrahydro-naphthalen-1-yloxy)-acetic acid tert-butyl ester (V, prepared as described above) was added, and the reaction mixture was stirred at 42° C. internal temperature. Upon gas evolution and foaming, the reaction mixture was cooled to 33° C. internal temperature over 1 hour, and then stirred for an additional 24 hours at 33° C. The reaction mixture was then cooled in an ice-water bath, diluted with 50 mL of de-ionized water, and extracted with 100 mL of toluene. The organic layer was separated and washed with 1 M aqueous citric acid (50 mL), saturated aqueous sodium bicarbonate (50 mL), and water (50 mL). The organic phase was then dried over MgSO4, and concentrated azeotropically at 35° C./20 mmHg to a total volume of 30 mL. The resulting solution was co-evaporated with 2×100 mL of toluene to a total volume of 20 mL (product and toluene), which was used in the next step without further purification.

Workup

  1. stirringthe reaction mixture was stirred at 42° C. internal temperature
  2. temperatureUpon gas evolution and foaming, the reaction mixture was cooled to 33° C. internal temperature over 1 hour
  3. stirringstirred for an additional 24 hours at 33° C
  4. temperatureThe reaction mixture was then cooled in an ice-water bath
  5. extractionextracted with 100 mL of toluene
  6. customThe organic layer was separated
  7. washwashed with 1 M aqueous citric acid (50 mL), saturated aqueous sodium bicarbonate (50 mL), and water (50 mL)
  8. dry with materialThe organic phase was then dried over MgSO4
  9. concentrationconcentrated azeotropically at 35° C./20 mmHg to a total volume of 30 mL
  10. customwas used in the next step without further purification

Sources & evidence

ORD record
ord-101ecad9f8294c9b96dde4cef3cdc8c2
Source dataset
uspto-grants-2012_04
Patent number
US08163781B2

Reaction notes

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