Methanol → (3S,4aR,4bS,6S,8R,8aR,10aR)-3-Furan-3-yl-6-isobutyryloxy-4a,8a-dimethyl-1,5-dioxo-dodecahydro-2-oxa-phenanthrene-8-carboxylic acid methyl ester

HRID 12326Notes

Reaction equation

HRID 12326 reaction equation
[CH3:1][O:2][C:3]([C@@H:5]1[CH2:18][C@H:17](N)[C:16](=[O:20])[C@H:15]2[C@@:6]1([CH3:28])[CH2:7][CH2:8][C@@H:9]1[C@:14]2([CH3:21])[CH2:13][C@@H:12]([C:22]2[CH:26]=[CH:25][O:24][CH:23]=2)[O:11][C:10]1=[O:27])=[O:4].[C:29](Cl)(=[O:36])[C:30]1[CH:35]=CC=C[CH:31]=1.C[OH:39]>CN(C1C=CN=CC=1)C.C(Cl)Cl>[CH3:1][O:2][C:3]([C@@H:5]1[CH2:18][C@H:17]([O:39][C:29](=[O:36])[CH:30]([CH3:35])[CH3:31])[C:16](=[O:20])[C@H:15]2[C@@:6]1([CH3:28])[CH2:7][CH2:8][C@@H:9]1[C@:14]2([CH3:21])[CH2:13][C@@H:12]([C:22]2[CH:26]=[CH:25][O:24][CH:23]=2)[O:11][C:10]1=[O:27])=[O:4]

Participants

6

Reactant 3

HCID 887MethanolHCID 7412Benzoyl chlorideHCID 44415859(2S,4aR,6aR,7R,9S,10aS,10bR)-9-(Amino)-2-(3-furanyl)-dodecahydro-6a,10b-dimethyl-4,10-dioxo-2H-naphtho[2,1-c]pyran-7-carboxylic acid methyl ester

Product 1

HCID 11419799(3S,4aR,4bS,6S,8R,8aR,10aR)-3-Furan-3-yl-6-isobutyryloxy-4a,8a-dimethyl-1,5-dioxo-dodecahydro-2-oxa-phenanthrene-8-carboxylic acid methyl esterYield 67%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

A solution of 39 (0.10 g, 0.26 mmol), benzoyl chloride (0.11 g, 0.78 mmol) and DMAP (0.08 g, 0.78 mmol) in CH2Cl2 (20 mL) was stirred at room temperature for 2 h. Absolute MeOH (15 mL) was added and the solvent was removed under reduced pressure. CH2Cl2 (25 mL) was added to the residue and the solution was washed with 10% HCl (2×20 mL), H2O (3×20 mL), and saturated NaCl (3×20 mL) and dried (Na2SO4). Removal of the solvent under reduced pressure afforded 0.09 g (67%) of 10 as a white crystalline solid, mp 155-157° C. (EtOAc/n-hexanes); 1H NMR (CDCl3): δ 1.44 (3H, s); 1.50 (3H, s); 1.63 (3H, m); 1.82 (1H, dd, J=2.1, 10.5); 2.0 (1H, m); 2.12 (1H, dd, J=2.7, 8.4); 2.17 (1H, m); 2.32 (1H, s); 2.48 (1H, dd, J=5.4, 13.2); 2.79 (1H, dd, J=3.3, 6.9); 2.87 (1H, dd, J=2.7, 13.5); 3.71 (3H, s); 4.69 (1H, m); 5.55 (1H, dd, J=5.1, 11.4); 6.37 (1H, dd, J=0.9, 1.8); 7.1 (1H, d, J=6.0); 7.39 (1H, t, J=1.8); 7.41 (1H, dd, J=0.9, 1.8); 7.46 (1H, m); 7.53 (1H, tt, J=1.5, 2.7, 7.2); 7.80 (1H, t, J=2.4); 7.82 (1H, t, J=1.2.

Workup

  1. customthe solvent was removed under reduced pressure
  2. additionCH2Cl2 (25 mL) was added to the residue
  3. washthe solution was washed with 10% HCl (2×20 mL), H2O (3×20 mL), and saturated NaCl (3×20 mL)
  4. dry with materialdried (Na2SO4)
  5. customRemoval of the solvent under reduced pressure

Sources & evidence

ORD record
ord-c3231ec3b7b04f169d839bf51b685ede
Source dataset
uspto-grants-2010_06
Patent number
US07728001B2

Reaction notes

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