Sodium borohydride → HCID 86690374, compound

HRID 513886Notes

Reaction equation

HRID 513886 reaction equation
[C:1]([O:4][C@H:5]1[CH2:22][CH2:21][C@@:20]2([CH3:23])[C@@H:7]([CH2:8][CH2:9][C@:10]3([CH3:37])[C@@H:19]2[CH2:18][CH2:17][C@H:16]2[C@@:11]3([CH3:36])[CH2:12][CH2:13][C@@:14]3([CH2:31][CH2:32][N+:33]([O-])=O)[CH2:26][C:25](=[O:27])[C:24]([CH:28]([CH3:30])[CH3:29])=[C:15]32)[C:6]1([CH3:39])[CH3:38])(=[O:3])[CH3:2].[BH4-].[Na+]>CO.CCOC(C)=O.[Ni](Cl)Cl>[C:1]([O:4][C@H:5]1[CH2:22][CH2:21][C@@:20]2([CH3:23])[C@@H:7]([CH2:8][CH2:9][C@:10]3([CH3:37])[C@@H:19]2[CH2:18][CH2:17][C@H:16]2[C@@:11]3([CH3:36])[CH2:12][CH2:13][C@@:14]3([CH2:31][CH2:32][NH2:33])[CH2:26][C:25](=[O:27])[C:24]([CH:28]([CH3:30])[CH3:29])=[C:15]32)[C:6]1([CH3:38])[CH3:39])(=[O:3])[CH3:2]

Participants

6

Reactant 2

HCID 4311764Sodium borohydrideHCID 86690375HCID 86690375, compound

Product 1

HCID 86690374HCID 86690374, compoundYield 68.4%

Reagents, catalysts & solvents 3

HCID 24385Nickel DichlorideCatalystHCID 887MethanolSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of (3aR,5aR,5bR,7aR,9S,11aR,11bR,13aS)-1-isopropyl-5a,5b,8,8,11a-pentamethyl-3a-(2-nitroethyl)-2-oxo-3,3a,4,5,5a,5b,6,7,7a,8,9,10,11,11a,11b,12,13,13a-octadecahydro-2H-cyclopenta[a]chrysen-9-yl acetate (27) (10 g, 18.46 mmol) and nickel(II) chloride (7.18 g, 55.4 mmol) in methanol (100 ml) was added sodium borohydride (6.98 g, 185 mmol) portionwise during 1 hour. The reaction mixture was stirred at 0° C. for 1 h. The mixture was diluted with EtOAc (250 mL). The organic phase was washed with sat. NH4Cl (50 mL) until the organic layer change to colorless. The combined organic layers were dried over anhydrous Na2SO4, and concentrated in vacuo to get the crude product (3aR,5aR,5bR,7aR,9S,11aR,11bR,13aS)-3a-(2-aminoethyl)-1-isopropyl-5a,5b,8,8,11a-pentamethyl-2-oxo-3,3a,4,5,5a,5b,6,7,7a,8,9,10,11,11a,11b,12,13,13a-octadecahydro-2H-cyclopenta[a]chrysen-9-yl acetate (34) (7 g, 12.63 mmol, 68.4% yield), which was used without further purification. 1H NMR (400 MHz, CHLOROFORM-d) δ=9.15 (dd, J=4.9, 11.4 Hz, 1H), 8.12 (br. s., 2H), 7.97-7.81 (m, 1H), 7.63-7.49 (m, 1H), 7.26-7.15 (m, 1H), 7.15-7.04 (m, 1H), 6.98 (d, J=18.6 Hz, 1H), 6.81-5.38 (m, 47H); LC/MS: m/z calculated 511.4. found 512.3 (M+1)+.

Workup

  1. washThe organic phase was washed with sat. NH4Cl (50 mL) until the organic layer change to colorless
  2. dry with materialThe combined organic layers were dried over anhydrous Na2SO4
  3. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-6dea1c376fa74120baa63a54acec5cbe
Source dataset
uspto-grants-2015_08
Patent number
US09102685B2

Reaction notes

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