Acetic Acid → (2S,4aR,6aR,7R,9S,10aS,10bR)-9-(Azido)-2-(3-furanyl)-dodecahydro-6a,10b-dimethyl-4,10-dioxo-2H-naphtho[2,1-c]pyran-7-carboxylic acid methyl ester

HRID 12323Notes

Reaction equation

HRID 12323 reaction equation
[CH3:1][O:2][C:3]([C@@H:5]1[CH2:18][C@@H:17](Br)[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].[N-:29]=[N+:30]=[N-:31].[Na+].C(O)(=O)C.O>CN(C=O)C>[CH3:1][O:2][C:3]([C@@H:5]1[CH2:18][C@H:17]([N:29]=[N+:30]=[N-: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 4

HCID 176Acetic AcidHCID 962WaterHCID 33557Sodium AzideHCID 68683634(2S,4aS,6aR,7R,9R,10aS,10bR)-9-(Bromo)-2-(3-furanyl)-dodecahydro-6a,10b-dimethyl-4,10-dioxo-2H-naphtho[2,1-c]pyran-7-carboxylic acid methyl ester

Product 1

HCID 11531750(2S,4aR,6aR,7R,9S,10aS,10bR)-9-(Azido)-2-(3-furanyl)-dodecahydro-6a,10b-dimethyl-4,10-dioxo-2H-naphtho[2,1-c]pyran-7-carboxylic acid methyl esterYield 87.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 36 (0.10 g, 0.22 mmol), sodium azide (0.05 g, 0.77 mmol) and glacial acetic acid in DMF (3 mL) was stirred at room temperature for 4 h. H2O (30 mL) was added and the mixture was extracted with EtOAc (20 mL). The EtOAc solution was washed with H2O (2×20 mL) and saturated NaCl (20 mL) and dried (Na2SO4). Removal of the solvent under reduced pressure afforded a crude solid. The crude solid was purified by column chromatography (eluent: 30% EtOAc/n-hexanes) to afford 0.08 g (86%) of 38 as a white solid, mp 200-203° C. (EtOAc/n-hexanes); 1H NMR (CDCl3): δ 1.13 (3H, s); 1.48 (3H, s); 1.68 (5H, m); 2.14 (31H, m); 2.34 (1H, ddd, J=3.6, 7.2, 27); 2.60 (1H, dd, J=5.1, 13.2); 2.72 (1H, dd, J=3.3, 13.2); 3.74 (3H, s); 3.92 (1H, dd, J=7.5, 12.6), 5.56 (1H, dd, J=5.1, 11.7); 6.39 (1H, dd, J=0.9, 1.8); 7.41 (1H, dd, J=1.2, 2.1); 7.43 (1H, dd, J=0.9, 1.5).

Workup

  1. extractionthe mixture was extracted with EtOAc (20 mL)
  2. washThe EtOAc solution was washed with H2O (2×20 mL) and saturated NaCl (20 mL)
  3. dry with materialdried (Na2SO4)
  4. customRemoval of the solvent under reduced pressure
  5. customafforded a crude solid
  6. customThe crude solid was purified by column chromatography (eluent: 30% EtOAc/n-hexanes)

Sources & evidence

ORD record
ord-1fe8c4491a6241759a422c3930951f7d
Source dataset
uspto-grants-2010_06
Patent number
US07728001B2

Reaction notes

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