Trifluoroacetic acid → 4-[(1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-[(2-acetamidoethylamino)methyl]-1-isopropenyl-5a,5b,8,8,11a-pentamethyl-1,2,3,4,5,6,7,7a,11,11b,12,13,13a,13b-tetradecahydrocyclopenta[a]chrysen-9-yl]benzoic acid

HRID 405063Notes

Reaction equation

HRID 405063 reaction equation
[C:1]([NH:4][CH2:5][CH2:6][NH:7][CH2:8][C@:9]12[CH2:47][CH2:46][C@@H:45]([C:48]([CH3:50])=[CH2:49])[C@@H:10]1[C@@H:11]1[C@@:24]([CH3:27])([CH2:25][CH2:26]2)[C@@:23]2([CH3:28])[C@@H:14]([C@:15]3([CH3:44])[C@@H:20]([CH2:21][CH2:22]2)[C:19]([CH3:30])([CH3:29])[C:18]([C:31]2[CH:43]=[CH:42][C:34]([C:35]([O:37]C(C)(C)C)=[O:36])=[CH:33][CH:32]=2)=[CH:17][CH2:16]3)[CH2:13][CH2:12]1)(=[O:3])[CH3:2].C(O)(C(F)(F)F)=O>C(Cl)Cl>[C:1]([NH:4][CH2:5][CH2:6][NH:7][CH2:8][C@:9]12[CH2:47][CH2:46][C@@H:45]([C:48]([CH3:50])=[CH2:49])[C@@H:10]1[C@@H:11]1[C@@:24]([CH3:27])([CH2:25][CH2:26]2)[C@@:23]2([CH3:28])[C@@H:14]([C@:15]3([CH3:44])[C@@H:20]([CH2:21][CH2:22]2)[C:19]([CH3:30])([CH3:29])[C:18]([C:31]2[CH:43]=[CH:42][C:34]([C:35]([OH:37])=[O:36])=[CH:33][CH:32]=2)=[CH:17][CH2:16]3)[CH2:13][CH2:12]1)(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 6422Trifluoroacetic acidHCID 86676405HCID 86676405, compound

Product 1

HCID 601526224-[(1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-[(2-acetamidoethylamino)methyl]-1-isopropenyl-5a,5b,8,8,11a-pentamethyl-1,2,3,4,5,6,7,7a,11,11b,12,13,13a,13b-tetradecahydrocyclopenta[a]chrysen-9-yl]benzoic acidYield 38.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((2-acetamidoethylamino)methyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoate (114 mg, 0.167 mmol) in DCM (1 ml) was added TFA (0.4 ml, 5.19 mmol). The mixture was stirred at rt for 3.5 h then was concentrated under reduced pressure. The residue was dissolved in dioxane and MeOH and was purified by pre. HPLC. The fractions containing the expected product were combined and concentrated under reduced pressure to afford the title compound as an off-white solid (40.7 mg, 0.065 mmol, 38.8% yield). LCMS: m/e 629.5 (M+H)+, 2.17 min (method 6). 1H NMR (500 MHz, Acetic) δ ppm 8.03 (d, J=8.24 Hz, 2H),7.30 (d, J=8.24 Hz, 2H), 5.37 (d, J=4.58 Hz, 1H), 4.79 (s, 1H), 4.68 (s, 1H), 3.61-3.70 (m, 2H), 3.40-3.53 (m, 2H), 3.37 (d, J=13.12 Hz, 1H), 2.98 (d, J=12.82 Hz, 1H), 2.49-2.57 (m, 1H), 2.09 (s, 3H), 1.75 (s, 3H), 1.19 (s, 3H), 1.14-2.24 (m, 22H), 1.10 (s, 3H), 1.07 (s, 3H), 1.02 (s, 3H), 1.00 (s, 3H).

Workup

  1. concentrationthen was concentrated under reduced pressure
  2. dissolutionThe residue was dissolved in dioxane
  3. customMeOH and was purified by pre
  4. additionThe fractions containing the expected product
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-97b452506d554deda8d1db7cf44aff67
Source dataset
uspto-grants-2014_06
Patent number
US08748415B2

Reaction notes

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