Trifluoroacetic acid → (S)-5-(4-Methoxy-benzenesulfonyl)-6-methyl-5,6-dihydrophenanthridine

HRID 2224625Notes

Reaction equation

HRID 2224625 reaction equation
O[C@@H:2]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[NH:16][S:17]([C:20]1[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=1)(=[O:19])=[O:18])[CH3:3].CC(OC(/N=N/C(OC(C)(C)C)=O)=O)(C)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.FC(F)(F)C(O)=O.C(=O)(O)[O-].[Na+]>O1CCCC1>[CH3:27][O:26][C:23]1[CH:22]=[CH:21][C:20]([S:17]([N:16]2[C@@H:2]([CH3:3])[C:4]3[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=3)[C:10]3[CH:15]=[CH:14][CH:13]=[CH:12][C:11]2=3)(=[O:18])=[O:19])=[CH:25][CH:24]=1

Participants

7

Reactant 5

HCID 6422Trifluoroacetic acidHCID 11776Triphenylphosphine2×HCID 516892Sodium BicarbonateHCID 6034084Di-tert-butyl diazene-1,2-dicarboxylate2×HCID 58597407N-[(R)-2'-(1-Hydroxy-ethyl)-biphenyl-2-yl]-4-methoxy-benzenesulfonamide

Product 1

HCID 58597406(S)-5-(4-Methoxy-benzenesulfonyl)-6-methyl-5,6-dihydrophenanthridine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

N-[(R)-2′-(1-Hydroxy-ethyl)-biphenyl-2-yl]-4-methoxy-benzenesulfonamide (0.04 g, 0.10 mmol) was dissolved in tetrahydrofuran (10 mL) and cooled to 0° C. Di-tert-butylazodicarboxylate (0.05 g, 0.21 mmol) and triphenylphosphine (0.06 g, 0.21 mmol) were added. After four hours, additional di-tert-butylazodicarboxylate (0.05 g, 0.21 mmol) and triphenylphosphine (0.06 g, 0.21 mmol) were added. The mixture was warmed to room temperature and stirred for 36 hours. Trifluoroacetic acid (2.5 mnL) was added and the mixture was stirred for two hours. A solution of saturated, aqueous sodium bicarbonate was added (100 niL) and the resulting mixture was extracted with diethyl ether (5×20 mL). The combined organic extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo to yield an oil. The resulting oil solidified upon standing. The title compound was evaluated by chiral stationary phase HPLC (Chiralpak AD-25×0.46 cm column) on a Rainin Auto-Prep System using 90:10 hexane:isopropanol as the eluding solvent with a 0.8 mL/min flow rate. HPLC analysis showed the product to be a 95:5 mixture of enantiorners where the S enantiomer was the major product.

Workup

  1. temperatureThe mixture was warmed to room temperature
  2. stirringthe mixture was stirred for two hours
  3. extractionthe resulting mixture was extracted with diethyl ether (5×20 mL)
  4. dry with materialThe combined organic extracts were dried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customto yield an oil

Sources & evidence

ORD record
ord-716e0bd2645d445faecbc80af2a51f53
Source dataset
uspto-grants-2008_05
Patent number
US07378427B2

Reaction notes

Loading…