Hippuristanol → HCID 49864735, compound

HRID 1677836Notes

Reaction equation

HRID 1677836 reaction equation
[CH3:1][C@@H:2]1[C:31]([CH3:33])([CH3:32])[O:30][C@:4]2([O:8][C@H:7]3[CH2:9][C@H:10]4[C@@H:15]5[CH2:16][CH2:17][C@H:18]6[CH2:23][C@H:22]([OH:24])[CH2:21][CH2:20][C@:19]6([CH3:25])[C@H:14]5[C@@H:13]([OH:26])[CH2:12][C@:11]4([CH3:27])[C@H:6]3[C@:5]2([OH:29])[CH3:28])[CH2:3]1>N1C=CC=CC=1.O=[Cr](=O)(O[Cr](=O)([O-])=O)[O-].[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1.CCOCC>[CH3:1][C@@H:2]1[C:31]([CH3:32])([CH3:33])[O:30][C@:4]2([O:8][C@H:7]3[CH2:9][C@H:10]4[C@@H:15]5[CH2:16][CH2:17][C@H:18]6[CH2:23][C@H:22]([OH:24])[CH2:21][CH2:20][C@:19]6([CH3:25])[C@H:14]5[C:13](=[O:26])[CH2:12][C@:11]4([CH3:27])[C@H:6]3[C@:5]2([OH:29])[CH3:28])[CH2:3]1.[CH3:1][C@@H:2]1[C:31]([CH3:32])([CH3:33])[O:30][C@:4]2([O:8][C@H:7]3[CH2:9][C@H:10]4[C@@H:15]5[CH2:16][CH2:17][C@H:18]6[CH2:23][C:22](=[O:24])[CH2:21][CH2:20][C@:19]6([CH3:25])[C@H:14]5[C:13](=[O:26])[CH2:12][C@:11]4([CH3:27])[C@H:6]3[C@:5]2([OH:29])[CH3:28])[CH2:3]1

Participants

6

Reactant 1

HCID 9981822Hippuristanol

Product 2

HCID 49864734HCID 49864734, compoundYield 28%HCID 49864735HCID 49864735, compoundYield 56%

Reagents, catalysts & solvents 3

HCID 1049PyridineSolventHCID 3283Diethyl EtherSolventHCID 2724130Cornforth reagentSolvent

Procedure

Oxidation of hippuristanol (1) to yield hippuristanol 11-one (4) and hippuristanol 3, 11-dione (5). To an ice-cooled solution of hippuristanol (1, 31.7 mg) in pyridine (0.5 mL), Cornforth reagent (0.7 mL) was added dropwise. The mixture was kept stirring for 30 min. in an ice bath, then 3 hr at RT. The mixture was taken up in ether and the suspension was filtered. The filtrate was washed with dilute hydrochloric acid, dried over Na2SO4, and concentrated. The resulting product was separated on silica TLC (CHCl3/EtOAc, 3:1, v/v) to give 8.8 mg of hippuristanol 11-one (4, 28%) and 17.7 mg of hippuristanol 3,11-dione (5, 56%). Hippuristanol 3,11-dione (5). white crystals. mp 181-183.5° C.; 1H NMR (CDCl3) δ 4.42 (m, 2H), 3.02 (s, 1H), 2.82 (ddd, J=13.0, 6.5, 2.0 Hz, 1H), 2.63 (d, J=12.0 Hz, 1H), 2.45 (dt, J=6.5, 14.5 Hz, 1H), 2.37 (dd, J=13.0, 8.0 Hz, 1H), 1.31 (s, 3H), 1.22 (s, 6H), 1.20 (s, 3H), 1.11 (s, 3H), 0.99 (d, J=7.0 Hz, 3H); 13C NMR (CDCl3) δ 211.6, 210.0, 115.0, 84.9, 80.4, 79.1, 63.9, 63.4, 58.8, 54.5, 46.9, 46.3, 44.3, 41.8, 40.5, 38.0, 37.0, 35.5, 35.2, 33.7, 32.4, 28.7, 28.5, 28.2, 23.0, 17.3, 14.8, 11.0; IR (KBr) 3510, 1695 cm−1; EIMS m/z 458 (M+, 5), 316 (92), 84 (100%).

Workup

  1. additionwas added dropwise
  2. custom3 hr
  3. customat RT
  4. filtrationthe suspension was filtered
  5. washThe filtrate was washed with dilute hydrochloric acid
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customThe resulting product was separated on silica TLC (CHCl3/EtOAc, 3:1

Sources & evidence

ORD record
ord-c35980a653c54caf8eb75a8521aa20ad
Source dataset
uspto-grants-2011_08
Patent number
US08008346B2

Reaction notes

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