Sodium Hydroxide → 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(2-(2-hydroxyethylsulfonyl)ethylamino)-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)benzoic acid

HRID 85615Notes

Reaction equation

HRID 85615 reaction equation
[CH3:1][C@:2]12[C@@:19]3([CH3:20])[C@@H:10]([C@:11]4([CH3:33])[C@@H:16]([CH2:17][CH2:18]3)[C:15]([CH3:22])([CH3:21])[C:14]([C:23]3[CH:32]=[CH:31][C:26]([C:27]([O:29]C)=[O:28])=[CH:25][CH:24]=3)=[CH:13][CH2:12]4)[CH2:9][CH2:8][C@@H:7]1[C@H:6]1[C@H:34]([C:37]([CH3:39])=[CH2:38])[CH2:35][CH2:36][C@:5]1([NH:40][CH2:41][CH2:42][S:43]([CH:46]=[CH2:47])(=[O:45])=[O:44])[CH2:4][CH2:3]2.[OH-:48].[Na+]>O1CCOCC1>[OH:48][CH2:47][CH2:46][S:43]([CH2:42][CH2:41][NH:40][C@:5]12[CH2:36][CH2:35][C@@H:34]([C:37]([CH3:39])=[CH2:38])[C@@H:6]1[C@@H:7]1[C@@:2]([CH3:1])([CH2:3][CH2:4]2)[C@@:19]2([CH3:20])[C@@H:10]([C@:11]3([CH3:33])[C@@H:16]([CH2:17][CH2:18]2)[C:15]([CH3:22])([CH3:21])[C:14]([C:23]2[CH:24]=[CH:25][C:26]([C:27]([OH:29])=[O:28])=[CH:31][CH:32]=2)=[CH:13][CH2:12]3)[CH2:9][CH2:8]1)(=[O:45])=[O:44]

Participants

4

Reactant 2

HCID 14798Sodium HydroxideHCID 86676584methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-3a-(2-(vinylsulfonyl)ethylamino)-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

Product 1

HCID 683579204-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(2-(2-hydroxyethylsulfonyl)ethylamino)-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)benzoic acidYield 55.3%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
78 °C

Procedure

A mixture of methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-3a-(2-(vinylsulfonyl)ethylamino)-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 (25 mg, 0.038 mmol) and sodium hydroxide (0.189 mL, 0.189 mmol) in dioxane (1 mL) was heated at 78° C. for 3 h. The reaction mixture was filtered and the clear solution was purified by prep HPLC to provide the title compound as a white solid (14 mg, 53%). LCMS: m/e 666.39 (M+H)+, 2.48 min (method 10). 1H NMR (500 MHz, Acetic acid d4) δ ppm 8.03 (d, J=8.24 Hz, 2H), 7.30 (d, J=8.24 Hz, 2H), 5.37 (d, J=4.27 Hz, 1H), 4.87 (s, 1H), 4.75 (s, 1H), 4.31-4.01 (m, 3H), 3.93-3.74 (m, 3H), 3.68-3.41 (m, 2H), 3.06-2.73 (m, 1H), 2.48-1.26 (m, 22H), 1.76 (s, 3H), 1.23 (s, 3H), 1.14 (s, 3H), 1.09 (s, 3H), 1.02 (s, 3H), 1.00 (s, 3H).

Workup

  1. filtrationThe reaction mixture was filtered
  2. customthe clear solution was purified by prep HPLC

Sources & evidence

ORD record
ord-983808d8d7584533911d9942753ff3c7
Source dataset
uspto-grants-2014_09
Patent number
US08846647B2

Reaction notes

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