Trifluoroacetic acid → 4-[[(3aS,5aR,5bR,7aR,9S,11aR,11bR,13aS)-3a-[(E)-3-hydroxy-3-oxo-prop-1-enyl]-1-isopropyl-5a,5b,8,8,11a-pentamethyl-2-oxo-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3H-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxo-butanoic acid

HRID 524456Notes

Reaction equation

HRID 524456 reaction equation
C([O:5][C:6](=[O:49])[C:7]([CH3:48])([CH3:47])[CH2:8][C:9]([O:11][C@H:12]1[CH2:29][CH2:28][C@@:27]2([CH3:30])[C@@H:14]([CH2:15][CH2:16][C@:17]3([CH3:44])[C@@H:26]2[CH2:25][CH2:24][C@H:23]2[C@@:18]3([CH3:43])[CH2:19][CH2:20][C@@:21]3(/[CH:38]=[CH:39]/[C:40]([OH:42])=[O:41])[CH2:33][C:32](=[O:34])[C:31]([CH:35]([CH3:37])[CH3:36])=[C:22]32)[C:13]1([CH3:46])[CH3:45])=[O:10])(C)(C)C.FC(F)(F)C(O)=O>ClCCl>[C:40](/[CH:39]=[CH:38]/[C@:21]12[CH2:33][C:32](=[O:34])[C:31]([CH:35]([CH3:37])[CH3:36])=[C:22]1[C@@H:23]1[C@@:18]([CH3:43])([CH2:19][CH2:20]2)[C@@:17]2([CH3:44])[C@@H:26]([C@:27]3([CH3:30])[C@@H:14]([CH2:15][CH2:16]2)[C:13]([CH3:46])([CH3:45])[C@@H:12]([O:11][C:9](=[O:10])[CH2:8][C:7]([CH3:47])([CH3:48])[C:6]([OH:49])=[O:5])[CH2:29][CH2:28]3)[CH2:25][CH2:24]1)([OH:42])=[O:41]

Participants

4

Reactant 2

HCID 6422Trifluoroacetic acidHCID 117701488(E)-3-((3aS,5aR,5bR,7aR,9S,11aR,11bR,13aS)-9-((4-(Tert-butoxy)-3,3-dimethyl-4-oxobutanoyl)oxy)-1-isopropyl-5a,5b,8,8,11a-pentamethyl-2-oxo-3,3a,4,5,5a,5b,6,7,7a,8,9,10,11,11a,11b,12,13,13a-octadecahydro-2H-cyclopenta[a]chrysen-3a-yl)acrylic acid

Product 1

HCID 865750004-[[(3aS,5aR,5bR,7aR,9S,11aR,11bR,13aS)-3a-[(E)-3-hydroxy-3-oxo-prop-1-enyl]-1-isopropyl-5a,5b,8,8,11a-pentamethyl-2-oxo-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3H-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxo-butanoic acidYield 46.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
20 °C

Procedure

To a solution of (E)-3-((3aS,5aR,5bR,7aR,9S,11aR,11bR,13aS)-9-((4-(tert-butoxy)-3,3-dimethyl-4-oxobutanoyl)oxy)-1-isopropyl-5a,5b,8,8,11a-pentamethyl-2-oxo-3,3a,4,5,5a,5b,6,7,7a,8,9,10,11,11a,11b,12,13,13a-octadecahydro-2H-cyclopenta[a]chrysen-3a-yl)acrylic acid (200 mg, 0.294 mmol) in dichloromethane (6 mL) stirred at room temp was added trifluoroacetic acid (TFA) (3 mL). The reaction mixture was stirred at 20° C. for 1 h. The product was extracted with DCM (15 mL*3) and the residue was purified by preparative-HPLC to give the title compound (85 mg, 39%) as a white solid. 1H NMR (400 MHz, CHLOROFORM-d) δ=7.05 (d, J=16.1 Hz, 1H), 5.75 (d, J=16.3 Hz, 1H), 4.52 (dd, J=4.8, 11.3 Hz, 1H), 3.32-3.11 (m, 1H), 2.78-2.61 (m, 3H), 2.34-2.12 (m, 3H), 2.06-0.61 (m, 44H); LC/MS: m/z calculated 624.4. Found 625.3 (M+1)+.

Workup

  1. extractionThe product was extracted with DCM (15 mL*3)
  2. customthe residue was purified by preparative-HPLC

Sources & evidence

ORD record
ord-c9814c0143f447ddb4e46ca51b8b6cdb
Source dataset
uspto-grants-2016_05
Patent number
US09340513B2

Reaction notes

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