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

HRID 12319

Reaction equation

HRID 12319 reaction equation
[CH3:1][O:2][C:3]([C@@H:5]1[CH2:18][C@H:17]([OH:19])[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[Si](Cl)(C)C.[C:34]1([N:40]=[C:41]=[O:42])[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1>C(Cl)Cl>[CH3:1][O:2][C:3]([C@@H:5]1[CH2:18][C@H:17]([O:19][C:41](=[O:42])[NH:40][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[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

5

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 7672Phenyl isocyanateHCID 11395172(2S,4aS,6aR,7R,9S,10aS,10bR)-9-(hydroxy)-2-(3-furanyl)dodecahydro-6a,10b-dimethyl-4,10-dioxo-2H-naphtho[2,1-c]pyran-7-carboxylic acid methyl ester

Product 1

HCID 11191431(3S,4aR,4bS,6S,8R,8aR,10aR)-3-Furan-3-yl-4a,8a-dimethyl-1,5-dioxo-6-phenylcarbamoyloxy-dodecahydro-2-oxa-phenanthrene-8-carboxylic acid methyl esterYield 14%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 8a (0.06 g, 0.14 mmol), trimethylsilyl chloride (0.01 mL, 0.08 mmol) and phenylisocyanate (0.1 mL, 0.92 mmol) in CH2Cl2 was stirred at room temperature for 5 days. The reaction mixture was then washed with saturated NaHCO3 (10 mL) and H2O (10 mL) and dried (Na2SO4). The solvent was removed under reduced pressure to give a crude oil. The oil was purified by column chromatography (eluent: ethyl acetate/n-hexanes) to afford 22 (0.01 g, 14%) as a clear oil: 1H NMR (CDCl3): δ 1.15 (s, 3H); 1.48 (s, 3H); 1.52-1.72 (m, 3H); 1.82 (dd, 1H, 2.7, 10.2 1H); 2.03-2.20 (m, 1H); 2.22 (s, 1H); 2.24-2.48 (m, 2H); 2.54 (dd, Ja=5.1, Jb=13.5, 1H); 2.80 (dd, Ja=3.6, Jb=13.2, 1H); 3.75 (s, 3H); 5.21 (dd, Ja=7.8, Jb=12.3, 1H); 5.54 (dd, J=11.7, 1H); 6.40 (m, 1H), 6.69 (br s, 1H); 6.87 (br s, 1H); 7.12 (m, 2H); 7.28-7.45 (m, 5H).

Workup

  1. washThe reaction mixture was then washed with saturated NaHCO3 (10 mL) and H2O (10 mL)
  2. dry with materialdried (Na2SO4)
  3. customThe solvent was removed under reduced pressure
  4. customto give a crude oil
  5. customThe oil was purified by column chromatography (eluent: ethyl acetate/n-hexanes)

Sources & evidence

ORD record
ord-9edfd93c7b884bb8a336fb912c356863
Source dataset
uspto-grants-2010_06
Patent number
US07728001B2

Linked notes

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