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

HRID 12318

Reaction equation

HRID 12318 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].[Cl:29][C:30]([Cl:34])([Cl:33])[C:31]#[N:32]>ClC(Cl)C>[CH3:1][O:2][C:3]([C@@H:5]1[CH2:18][C@H:17]([O:19][C:31](=[NH:32])[C:30]([Cl:34])([Cl:33])[Cl:29])[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

4

Reactant 2

HCID 11011TrichloroacetonitrileHCID 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 11341622(3S,4aR,4bS,6S,8R,8aR,10aR)-3-Furan-3-yl-4a,8a-dimethyl-1,5-dioxo-6-(2,2,2-trichloro-acetimidoyloxy)-dodecahydro-2-oxa-phenanthrene-8-carboxylic acid methyl esterYield 37%

Reagents, catalysts & solvents 1

HCID 63651,1-DichloroethaneSolvent

Procedure

A solution of 8a (0.05 g, 0.13 mmol), trichloroacetonitrile (0.1 mL, 1.0 mmol), 1,8-Diazobicylo[5.4.0]undec-7-ene (0.05 mL, 0.3 mmol) in dichloroethane (20 mL) was stirred at 0° C. for 24 h. 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 21 (0.02 g, 37%) as a white solid, mp 120-123° C.; 1H NMR (CDCl3): δ 1.18 (s, 3H); 1.50 (s, 3H); 1.52-1.76 (m, 4H); 1.85 (dd, Ja=2.6, Jb=10.1, 1H); 2.10 (dd, Ja=2.9, Jb=11.6, 1H); 2.20 (m, 1H); 2.24 (s, 1H); 2.35-2.58 (m, 3H); 2.80 (dd, Ja=4.1, Jb=12.5, 1H); 3.75 (s, 3H); 5.34 (dd, Ja=7.7, Jb=12.2, 1H); 6.40 (dd, Ja=0.9, Jb=1.5, 1H); 7.41 (dd, 1H, 1.5, 1.5, 1H); 7.43 (dd, Ja=0.9, Jb=1.5, 1H); 8.38 (s, 1H).

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-aa8df4840fe94da7921b80707f1ba252
Source dataset
uspto-grants-2010_06
Patent number
US07728001B2

Linked notes

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