Triethylamine → (1R,3aS,5aR,5bR,7aR,11aR,11bR,13bR)-5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carbaldehyde

HRID 1401016Notes

Reaction equation

HRID 1401016 reaction equation
C(Cl)(=O)C(Cl)=O.[OH:7][CH2:8][C@:9]12[CH2:35][CH2:34][C@@H:33]([C:36]([CH3:38])=[CH2:37])[C@@H:10]1[CH:11]1[C@@:24]([CH3:27])([CH2:25][CH2:26]2)[C@@:23]2([CH3:28])[C@@H:14]([C@:15]3([CH3:32])[C@@H:20]([CH2:21][CH2:22]2)[C:19]([CH3:30])([CH3:29])[C@@H:18]([OH:31])[CH2:17][CH2:16]3)[CH2:13][CH2:12]1.C(N(CC)CC)C>C(Cl)Cl.CS(C)=O>[CH3:27][C@:24]12[C@@:23]3([CH3:28])[C@@H:14]([C@:15]4([CH3:32])[C@@H:20]([CH2:21][CH2:22]3)[C:19]([CH3:29])([CH3:30])[C:18](=[O:31])[CH2:17][CH2:16]4)[CH2:13][CH2:12][CH:11]1[C@H:10]1[C@H:33]([C:36]([CH3:38])=[CH2:37])[CH2:34][CH2:35][C@:9]1([CH:8]=[O:7])[CH2:26][CH2:25]2

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 51340201(1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysen-9-ol

Product 1

HCID 86692373(1R,3aS,5aR,5bR,7aR,11aR,11bR,13bR)-5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carbaldehydeYield 75.1%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolvent2×HCID 6344DichloromethaneSolvent3×

Procedure

To a 2M solution of oxalyl chloride (47.0 mL, 94 mmol) in CH2Cl2, was added a solution of DMSO (13.7 mL, 192 mmol) in CH2Cl2 (20 mL) dropwise at −15° C. After 5 min, a solution of (1R,3aS,5aR,5bR,7aR,9S,11aR,11bR,13bR)-3a-(hydroxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysen-9-ol (4.43 g, 10.01 mmol) in a mixture of DMSO (30 mL) and CH2Cl2 (50 mL) was added at −15° C. Triethylamine (56 mL) was added 15 minutes later and the stirring was continued for another 10 min. The reaction mixture was allowed to warm up to RT. The reaction was quenched by addition of water (100 mL), and the reaction mixture was extracted with CH2Cl2 (70 mL×3). The combined organic layers were washed with brine (30 mL×3), dried over MgSO4, filtered and concentrated. The crude material was purified using silica gel chromatography eluted with a mixture of ethyl acetate and hexanes, to give the product as a solid (3.3 g 75%). LCMS: m/e 461.15 (M+Na)+, 2.91 min (method 2).

Workup

  1. additionwas added at −15° C
  2. waitthe stirring was continued for another 10 min
  3. customThe reaction was quenched by addition of water (100 mL)
  4. extractionthe reaction mixture was extracted with CH2Cl2 (70 mL×3)
  5. washThe combined organic layers were washed with brine (30 mL×3)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude material was purified
  10. washeluted with a mixture of ethyl acetate and hexanes

Sources & evidence

ORD record
ord-caa6444f11754158afa9f21832555531
Source dataset
uspto-grants-2014_12
Patent number
US08906889B2

Reaction notes

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