Acetic Acid → methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(3-(tert-butoxycarbonylamino)propylamino)-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

HRID 85624Notes

Reaction equation

HRID 85624 reaction equation
C(O)(=O)C.O=[CH:6][CH2:7][CH2:8][NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13].[NH2:17][C@:18]12[CH2:53][CH2:52][C@@H:51]([C:54]([CH3:56])=[CH2:55])[C@@H:19]1[C@@H:20]1[C@@:33]([CH3:36])([CH2:34][CH2:35]2)[C@@:32]2([CH3:37])[C@@H:23]([C@:24]3([CH3:50])[C@@H:29]([CH2:30][CH2:31]2)[C:28]([CH3:39])([CH3:38])[C:27]([C:40]2[CH:49]=[CH:48][C:43]([C:44]([O:46][CH3:47])=[O:45])=[CH:42][CH:41]=2)=[CH:26][CH2:25]3)[CH2:22][CH2:21]1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>CCO.O1CCOCC1>[C:12]([O:11][C:10]([NH:9][CH2:8][CH2:7][CH2:6][NH:17][C@:18]12[CH2:53][CH2:52][C@@H:51]([C:54]([CH3:56])=[CH2:55])[C@@H:19]1[C@@H:20]1[C@@:33]([CH3:36])([CH2:34][CH2:35]2)[C@@:32]2([CH3:37])[C@@H:23]([C@:24]3([CH3:50])[C@@H:29]([CH2:30][CH2:31]2)[C:28]([CH3:38])([CH3:39])[C:27]([C:40]2[CH:41]=[CH:42][C:43]([C:44]([O:46][CH3:47])=[O:45])=[CH:48][CH:49]=2)=[CH:26][CH2:25]3)[CH2:22][CH2:21]1)=[O:16])([CH3:15])([CH3:14])[CH3:13]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 5049666Sodium triacetoxyborohydrideHCID 10910051tert-Butyl N-(3-oxopropyl)carbamateHCID 68357865methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-1-isopropenyl-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)benzoate

Product 1

HCID 86676589methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(3-(tert-butoxycarbonylamino)propylamino)-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)benzoateYield 54%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 312751,4-DioxaneSolvent

Procedure

Acetic acid (0.013 mL, 0.221 mmol) and tert-butyl 3-oxopropylcarbamate (38.2 mg, 0.221 mmol) were added to a solution of methyl 4-((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)benzoate (40 mg, 0.074 mmol) in EtOH (1 mL) and dioxane (1.0 mL) and the mixture was stirred for 2 h at rt. Sodium triacetoxyborohydride (78 mg, 0.368 mmol) was added and the reaction mixture was stirred at 20° C. for two hours. The reaction was quenched with a saturated aqueous solution of sodium bicarbonate (3 mL), washed with 0.1N HCl (5 mL) and brine (5 mL) and extracted with DCM (3×5 mL). All the extracts were combined, dried over sodium sulfate, filtered and concentrated under reduced pressure to provide the title compound as pale yellow oil (28 mg, 54%). LCMS: m/e 701.51 (M+H)+, 4.0 min (method 10).

Workup

  1. stirringthe reaction mixture was stirred at 20° C. for two hours
  2. customThe reaction was quenched with a saturated aqueous solution of sodium bicarbonate (3 mL)
  3. washwashed with 0.1N HCl (5 mL) and brine (5 mL)
  4. extractionextracted with DCM (3×5 mL)
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-0743c880fb7d47c1a2c6ac6a7da181f4
Source dataset
uspto-grants-2014_09
Patent number
US08846647B2

Reaction notes

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