Sodium Hydroxide → 2-[(1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-1-isopropenyl-5a,5b,8,8,11a-pentamethyl-3a-(2-morpholinoethylamino)-1,2,3,4,5,6,7,7a,11,11b,12,13,13a,13b-tetradecahydrocyclopenta[a]chrysen-9-yl]spiro[3.3]hept-2-ene-6,6-dicarboxylic acid

HRID 1401008Notes

Reaction equation

HRID 1401008 reaction equation
[CH3:1][C@:2]12[C@@:19]3([CH3:20])[C@@H:10]([C@:11]4([CH3:42])[C@@H:16]([CH2:17][CH2:18]3)[C:15]([CH3:22])([CH3:21])[C:14]([C:23]3[CH2:41][C:25]5([CH2:28][C:27]([C:35]([O:37]C(C)C)=[O:36])([C:29]([O:31]C(C)C)=[O:30])[CH2:26]5)[CH:24]=3)=[CH:13][CH2:12]4)[CH2:9][CH2:8][C@@H:7]1[C@H:6]1[C@H:43]([C:46]([CH3:48])=[CH2:47])[CH2:44][CH2:45][C@:5]1([NH:49][CH2:50][CH2:51][N:52]1[CH2:57][CH2:56][O:55][CH2:54][CH2:53]1)[CH2:4][CH2:3]2.[OH-].[Na+]>O1CCOCC1.CO>[CH3:1][C@:2]12[C@@:19]3([CH3:20])[C@@H:10]([C@:11]4([CH3:42])[C@@H:16]([CH2:17][CH2:18]3)[C:15]([CH3:21])([CH3:22])[C:14]([C:23]3[CH2:41][C:25]5([CH2:28][C:27]([C:29]([OH:31])=[O:30])([C:35]([OH:37])=[O:36])[CH2:26]5)[CH:24]=3)=[CH:13][CH2:12]4)[CH2:9][CH2:8][C@@H:7]1[C@H:6]1[C@H:43]([C:46]([CH3:48])=[CH2:47])[CH2:44][CH2:45][C@:5]1([NH:49][CH2:50][CH2:51][N:52]1[CH2:53][CH2:54][O:55][CH2:56][CH2:57]1)[CH2:4][CH2:3]2

Participants

5

Reactant 2

HCID 14798Sodium HydroxideHCID 86692359diisopropyl 6-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-3a-((2-morpholinoethyl)amino)-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)spiro[3.3]hept-5-ene-2,2-dicarboxylate

Product 1

HCID 865754152-[(1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-1-isopropenyl-5a,5b,8,8,11a-pentamethyl-3a-(2-morpholinoethylamino)-1,2,3,4,5,6,7,7a,11,11b,12,13,13a,13b-tetradecahydrocyclopenta[a]chrysen-9-yl]spiro[3.3]hept-2-ene-6,6-dicarboxylic acidYield 74%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of diisopropyl 6-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-3a-((2-morpholinoethyl)amino)-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)spiro[3.3]hept-5-ene-2,2-dicarboxylate (9 mg, 0.011 mmol) in 1,4-dioxane (1 mL) and MeOH (0.5 mL) was added 1N NaOH (0.5 mL, 0.500 mmol)). The mixture was stirred at 50° C. for 3 h. The crude product was purified by Prep HPLC using method 14 to give desired product in 74% yield as a solid. MS: m/e 703.6 (M+H)+, 2.42 min (method 4). 1H NMR (400 MHz, METHANOL-d4) δ 5.96 (s, 1H), 5.54 (dd, J=6.1, 1.6 Hz, 1H), 4.81 (s, 1H), 4.70 (s, 1H), 3.80-3.67 (m, 4H), 3.15-3.01 (m, 2H), 2.94-2.76 (m, 2H), 2.76-2.58 (m, 8H), 2.52 (br. s., 2H), 2.22-2.14 (m, 1H), 2.10-1.87 (m, 2H), 1.83-1.07 (m, 19H), 1.76 (s, 3H), 1.24 (s, 3H), 1.18 (s, 4H), 1.09 (s, 6H), 0.85 (s, 3H).

Workup

  1. customThe crude product was purified by Prep HPLC

Sources & evidence

ORD record
ord-c771b8a7c6c44404bdc4313b3ef55d4f
Source dataset
uspto-grants-2014_12
Patent number
US08906889B2

Reaction notes

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