Acetic Acid → HCID 86692323, compound

HRID 1400976Notes

Reaction equation

HRID 1400976 reaction equation
[NH2:1][C@:2]12[CH2:46][CH2:45][C@@H:44]([C:47]([CH3:49])=[CH2:48])[C@@H:3]1[C@@H:4]1[C@@:17]([CH3:20])([CH2:18][CH2:19]2)[C@@:16]2([CH3:21])[C@@H:7]([C@:8]3([CH3:43])[C@@H:13]([CH2:14][CH2:15]2)[C:12]([CH3:23])([CH3:22])[C:11]([C:24]2[CH2:42][C:26]4([CH2:29][C:28]([C:36]([O:38][CH:39]([CH3:41])[CH3:40])=[O:37])([C:30]([O:32][CH:33]([CH3:35])[CH3:34])=[O:31])[CH2:27]4)[CH:25]=2)=[CH:10][CH2:9]3)[CH2:6][CH2:5]1.C(O)(=O)C.[H][H]>C(O)C.O1CCOCC1.[OH-].[Pd+2].[OH-]>[NH2:1][C@:2]12[CH2:46][CH2:45][C@@H:44]([CH:47]([CH3:49])[CH3:48])[C@@H:3]1[C@@H:4]1[C@@:17]([CH3:20])([CH2:18][CH2:19]2)[C@@:16]2([CH3:21])[C@@H:7]([C@:8]3([CH3:43])[C@@H:13]([CH2:14][CH2:15]2)[C:12]([CH3:22])([CH3:23])[C:11]([CH:24]2[CH2:25][C:26]4([CH2:29][C:28]([C:30]([O:32][CH:33]([CH3:34])[CH3:35])=[O:31])([C:36]([O:38][CH:39]([CH3:40])[CH3:41])=[O:37])[CH2:27]4)[CH2:42]2)=[CH:10][CH2:9]3)[CH2:6][CH2:5]1

Participants

7

Reactant 3

HCID 176Acetic AcidHCID 86692314diisopropyl 6-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-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)spiro[3.3]hept-5-ene-2,2-dicarboxylateHCID 178418361HCID 178418361, compound

Product 1

HCID 86692323HCID 86692323, compoundYield 100%

Reagents, catalysts & solvents 3

HCID 9942167Palladium hydroxideCatalystHCID 702EthanolSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of diisopropyl 6-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-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)spiro[3.3]hept-5-ene-2,2-dicarboxylate (0.057 g, 0.085 mmol) in ethanol (2 mL), 1,4-dioxane (2 mL) and acetic acid (0.02 mL, 0.349 mmol) was added palladium hydroxide (20% on carbon) (0.072 g, 0.103 mmol). The mixture as stirred under 1 atm of hydrogen overnight. After stirring the mixture for 15 h, it was filtered through a plug of celite (washed with MeOH) then the filtrate was concentrated under reduced pressure. The residue was diluted with 15 mL of sat. aq. NaHCO3 and extracted with dichloromethane (3×15 mL). The combined organic layers were dried with sodium sulfate. The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure to give diisopropyl 6-((1S,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-1-isopropyl-5a,5b,8,8,11a-pentamethyl-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]heptane-2,2-dicarboxylate (0.057 g, 0.085 mmol, 100% yield) as an off-white solid. 1H NMR (500 MHz, chloroform-d) δ=5.33 (d, J=5.7 Hz, 1H), 5.11-5.02 (m, 2H), 3.80-3.72 (m, 1H), 3.68-3.60 (m, 1H), 2.66 (s, 2H), 2.44 (s, 2H), 2.99-0.64 (m, 62H).

Workup

  1. filtrationit was filtered through a plug of celite (washed with MeOH)
  2. concentrationthe filtrate was concentrated under reduced pressure
  3. additionThe residue was diluted with 15 mL of sat. aq. NaHCO3
  4. extractionextracted with dichloromethane (3×15 mL)
  5. dry with materialThe combined organic layers were dried with sodium sulfate
  6. customThe drying agent was removed by filtration
  7. concentrationthe filtrate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-02b70ca5550c455c8d65a681f362dd26
Source dataset
uspto-grants-2014_12
Patent number
US08906889B2

Reaction notes

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