Tetrahydrofuran → (1S,5R,7S,8S)-7-Hydroxy-4-methoxy-8-methyl-8-(4-methyl-4-((triethylsilyl)oxy)pentyl)-5-(3-methylbut-2-en-1-yl)bicyclo[3.3.1]non-3-ene-2,9-dione

HRID 633662ノート

反応式

HRID 633662 の反応式
C1COCC1.C(=S)(OC1C=CC=CC=1)[O:7][C@H:8]1[CH2:15][C@@:14]2([CH2:18][CH:19]=[C:20]([CH3:22])[CH3:21])[C:16](=[O:17])[C@H:10]([C:11](=[O:25])[CH:12]=[C:13]2[O:23][CH3:24])[C@:9]1([CH3:40])[CH2:26][CH2:27][CH2:28][C:29]([CH3:39])([O:31][Si:32]([CH2:37][CH3:38])([CH2:35][CH3:36])[CH2:33][CH3:34])[CH3:30].[Li]N1C(C)(C)CCCC1(C)C.CCCCCC>CCOC(C)=O>[OH:7][C@@H:8]1[C@@:9]([CH3:40])([CH2:26][CH2:27][CH2:28][C:29]([CH3:30])([O:31][Si:32]([CH2:35][CH3:36])([CH2:37][CH3:38])[CH2:33][CH3:34])[CH3:39])[C@@H:10]2[C:16](=[O:17])[C@@:14]([CH2:18][CH:19]=[C:20]([CH3:21])[CH3:22])([C:13]([O:23][CH3:24])=[CH:12][C:11]2=[O:25])[CH2:15]1

参加物

6

反応物 4

HCID 8028Tetrahydrofuran2 回HCID 8058HexaneHCID 90123985O-((1S,2S,3S,5R)-6-Methoxy-2-methyl-2-(4-methyl-4-((triethylsilyl)oxy)pentyl)-5-(3-methylbut-2-en-1-yl)-8,9-dioxobicyclo[3.3.1]non-6-en-3-yl) O-phenyl carbonothioateHCID 178418821HCID 178418821、化合物

生成物 1

HCID 71499450(1S,5R,7S,8S)-7-Hydroxy-4-methoxy-8-methyl-8-(4-methyl-4-((triethylsilyl)oxy)pentyl)-5-(3-methylbut-2-en-1-yl)bicyclo[3.3.1]non-3-ene-2,9-dione収率 79%

試薬・触媒・溶媒 1

HCID 8857Ethyl Acetate溶媒

反応条件

温度
-78 °C

実験手順

A THF (2 mL) solution of 40 (144 mg, 0.269 mmol, 1 equiv.) was cooled to −78° C. in a 25-mL recovery flask, and a freshly prepared THF solution of lithium tetramethylpiperidide (0.50 M, 2.2 mL, 1.1 mmol, 4 equiv.) was added. The resulting orange solution was stirred at −78° C. for 15 min and then stirred at 0° C. for 40 min. The reaction was then quenched with saturated aqueous NaHCO3 at 0° C. The mixture was warmed to room temperature and extracted thrice with EtOAc. The organic extracts were combined, washed with H2O and brine, dried over Na2SO4, filtered, and concentrated in vacuo to an orange oil. Flash column chromatography (75 mL SiO2, 7:3 hexane:EtOAc) afforded 104.3 mg (0.2117 mmol, 79% yield) of 41 as a faint yellow oil. TLC Rf 0.56 (1:1 hexane:EtOAc). 1H NMR (600 MHz; CDCl3): δ 5.63 (s, 1H), 4.95 (t, J=7.0 Hz, 1H), 3.78 (d, J=7.8 Hz, 1H), 3.73 (s, 3H), 3.15 (s, 1H), 2.47 (dd, J=14.5, 6.4 Hz, 1H), 2.37 (dd, J=14.5, 7.6 Hz, 1H), 2.09 (dd, J=13.4, 5.4 Hz, 1H), 1.88 (s, 1H), 1.73 (dd, J=13.3, 11.6 Hz, 1H), 1.65 (m, 7H), 1.52 (td, J=12.6, 3.5 Hz, 1H), 1.39 (td, J=12.5, 4.1 Hz, 1H), 1.34-1.27 (m, 2H), 1.23 (m, 4H), 1.18 (s, 3H), 0.92 (t, J=7.9 Hz, 9H), 0.86 (s, 3H), 0.54 (q, J=7.8 Hz, 6H). 13C NMR (126 MHz; CDCl3): δ 205.4, 193.1, 177.4, 134.4, 119.0, 105.9, 73.6, 72.0, 69.2, 57.0, 56.0, 46.2, 45.6, 39.4, 38.4, 30.6, 29.50, 29.48, 26.1, 18.1, 17.9, 15.7, 7.3, 6.9. HRMS-ESI (m/z): [M+Na]+ calculated for C28H48O5Si, 515.3163. found, 515.3170.

後処理

  1. stirringstirred at 0° C. for 40 min
  2. customThe reaction was then quenched with saturated aqueous NaHCO3 at 0° C
  3. temperatureThe mixture was warmed to room temperature
  4. extractionextracted thrice with EtOAc
  5. washwashed with H2O and brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo to an orange oil

出典と根拠

ORDレコード
ord-0039f294bba1464395441ef0ac856d90
出典データセット
uspto-grants-2016_04
特許番号
US09321713B2

反応ノート

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