(+)-Calanolide A → Calanolide

HRID 1637979Notes

Reaction equation

HRID 1637979 reaction equation
[CH3:1][CH2:2][CH2:3][C:4]1[C:10]2[C:11]3[O:25][C:24]([CH3:27])([CH3:26])[CH:23]=[CH:22][C:12]=3[C:13]3[O:18][C@H:17]([CH3:19])[C@@H:16]([CH3:20])[C@H:15]([OH:21])[C:14]=3[C:9]=2[O:8][C:6](=[O:7])[CH:5]=1.CCCC1C2C3OC(C)(C)C=CC=3C3O[C@@H](C)[C@H](C)[C@@H](O)C=3C=2OC(=O)C=1.CCCCCC.C(OCC)(=O)C>CCCCCC.C(O)C>[CH3:1][CH2:2][CH2:3][C:4]1[C:10]2[C:11]3[O:25][C:24]([CH3:27])([CH3:26])[CH:23]=[CH:22][C:12]=3[C:13]3[O:18][CH:17]([CH3:19])[CH:16]([CH3:20])[CH:15]([OH:21])[C:14]=3[C:9]=2[O:8][C:6](=[O:7])[CH:5]=1

Participants

5

Reactant 3

HCID 64972(+)-Calanolide AHCID 384854(-)-Calanolide AHCID 21226206Ethyl acetate hexane

Product 1

HCID 1201Calanolide

Reagents, catalysts & solvents 1

HCID 21879635Ethanol hexaneSolvent

Procedure

The synthetic (±)-1 was resolved into enantiomers, (+)-calanolide A and (-) calanolide A, by preparative HPLC. Thus, using a normal phase silica gel HPLC column (250 mm×4.6 mm I. D. Zorbasil, 5 μm particle size, MAC-MOD Analytical, Inc., PA, USA), the synthetic (±)-1 appeared as one peak with a retention time of 10.15 minutes when hexane/ethyl acetate (70:30) was used as the mobile phase at a flow rate of 1.5 mL/min and a wavelength of 290 nm was used as the uv detector setting. However, on a chiral HPLC column packed with amylose carbamate (250 mm×4.6 mm I. D. Chiralpak A D, 10 μm particle size, Chiral Technologies, Inc., PA, USA), two peaks with retention times of 6.39 and 7.15 minutes in a ratio of 1:1 were observed at a flow rate of 1.5 mL/min. The mobile phase was hexane/ethanol (95:5) and the uv detector was set at a wavelength of 254 nm. These two components were separated using a semi-preparative chiral HPLC column, providing the pure enantiomers of calanolide A. The chemical structures of the separated enantiomers, which were assigned based on their optical rotations and compared with the reported natural product, were characterized by spectroscopic data. HPLC chromatograms (±)-calanolide A and its optical forms are shown in FIG. 6.

Workup

  1. customThese two components were separated

Sources & evidence

ORD record
ord-92934215700440b99664a82e5989f2c3
Source dataset
uspto-grants-2000_03
Patent number
US06043271

Reaction notes

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