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

HRID 12317

反応式

HRID 12317 の反応式
[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].CCN(CC)CC.Cl[Si:37]([CH3:40])([CH3:39])[CH3:38]>C(Cl)Cl>[CH3:1][O:2][C:3]([C@@H:5]1[CH2:18][C@H:17]([O:19][Si:37]([CH3:40])([CH3:39])[CH3:38])[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]

参加物

5

反応物 3

HCID 6397ChlorotrimethylsilaneHCID 8471TriethylamineHCID 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

生成物 1

HCID 11167140(3S,4aR,4bS,6S,8R,8aR,10aR)-3-Furan-3-yl-4a,8a-dimethyl-1,5-dioxo-6-trimethylsilanyloxy-dodecahydro-2-oxa-phenanthrene-8-carboxylic acid methyl ester収率 68%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

A solution of 8a (0.08 g, 0.20 mmol), NEt3 (0.1 mL, 0.72 mmol) and chlorotrimethylsilane (0.1 mL, 0.79 mmol) in CH2Cl2 (30 mL) was stirred at room temperature overnight. The mixture was washed with saturated NaHCO3 (2×10 mL) and H20 (50 mL), dried (Na2SO4), and the solvent was removed under reduced pressure. The resulting crude solid was purified by column chromatography (eluent: ethyl acetate/nhexanes) to afford 16 (0.06 g, 68%) as a white solid, mp 197-200° C.; 1H NMR (CDCl3): δ 0.14 (9H, s, (CH3)3SiO; 1.11 (3H, s, H-19); 1.48 (3H, s, H-29); 1.50-1.73 (3H, m, H-7α,β and H-11β); 1.79 (1H, ddd, J=3.0, 3.0, 10.5 Hz, H-6α); 2.03 (1H, dd, obscured, H-8); 2.06 (1H, s, H-10); 2.10-2.38 (3H, m, H-3α,β and H-6β); 2.57 (1H, dd, J=5.1, 10.5 Hz, H-11α); 2.69 (1H, dd, J=3.9, 12.9 Hz, H-4); 3.72 (3H, s, CO2CH3); 4.12 (1H, dd, J=7.5, 11.7 Hz, H-2); 5.56 (1H, dd, J=5.1, 11.4 Hz, H-12); 6.38 (1H, dd, J=0.8, 1.7 Hz, H-14); 7.40 (1H, m, H-15); 7.42 (1H, m, H-16).

後処理

  1. washThe mixture was washed with saturated NaHCO3 (2×10 mL) and H20 (50 mL)
  2. dry with materialdried (Na2SO4)
  3. customthe solvent was removed under reduced pressure
  4. customThe resulting crude solid was purified by column chromatography (eluent: ethyl acetate/nhexanes)

出典と根拠

ORDレコード
ord-7caa50fd5b074b9d813eca73504ee6f7
出典データセット
uspto-grants-2010_06
特許番号
US07728001B2

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