Hydrochloric Acid → (R)-2-Methyl-2-(2-trimethylsilanyl-ethoxymethyl)-but-3-enoic acid

HRID 2285347ノート

反応式

HRID 2285347 の反応式
C([C@@H]1COC(=O)N1[C:10](=[O:23])[C@@:11]([CH3:22])([CH2:14][O:15][CH2:16][CH2:17][Si:18]([CH3:21])([CH3:20])[CH3:19])[CH:12]=[CH2:13])(C)C.OO.O.[OH-].[Li+].S(S([O-])=O)([O-])(=O)=[O:30].[Na+].[Na+].Cl>O1CCCC1.O>[CH3:22][C@:11]([CH2:14][O:15][CH2:16][CH2:17][Si:18]([CH3:19])([CH3:20])[CH3:21])([CH:12]=[CH2:13])[C:10]([OH:23])=[O:30]

参加物

7

反応物 5

HCID 313Hydrochloric AcidHCID 784Hydrogen PeroxideHCID 168937Lithium hydroxide, monohydrateHCID 656671Sodium PyrosulfiteHCID 86709642(R)-4-Isopropyl-3-[(R)-2-methyl-2-(2-trimethylsilanyl-ethoxymethyl)-but-3-enoyl]-oxazolidin-2-one

生成物 1

HCID 86709643(R)-2-Methyl-2-(2-trimethylsilanyl-ethoxymethyl)-but-3-enoic acid収率 88%

試薬・触媒・溶媒 1

HCID 21881883Oxolane--water (1/1)溶媒

反応条件

温度
0 °C

実験手順

A cooled (0° C.) solution of (R)-4-isopropyl-3-[(R)-2-methyl-2-(2-trimethylsilanyl-ethoxymethyl)-but-3-enoyl]-oxazolidin-2-one (543.3 mg, 1.591 mmol) in tetrahydrofuran/water (15 mL, 2:1) was subsequently treated with hydrogen peroxide (30%, 820 μL, 7.955 mmol) and lithium hydroxide monohydrate (133.5 mg, 3.181 mmol). After stirring at 0° C. for 2 h, the reaction was quenched with solid sodium metabisulfite (3 g, 16 mmol). After stirring at room temperature for 30 min, the mixture was acidified with hydrochloric acid (1 M) to pH 2, the aqueous layer was extracted with dichloromethane (2×). The organics were combined, filtered through a phase separator and the volatiles were removed in vacuo. The residue was purified by silica gel chromatography using a 50 g Isolute cartridge eluted with a continuous gradient of iso-hexanes/ethyl acetate 1:0 to 4:1 to afford the title compound (322.3 mg, 88%) as a colourless oil. 1H NMR (300 MHz, CDCl3) δ 0.03 (s, 9H), 0.98 (app t, J=8.5 Hz, 2H), 1.34 (s, 3H), 3.46 (d, J=8.9 Hz, 1H), 3.57-3.67 (m, 3H), 5.19-5.29 (m, 2H), 6.00 (dd, J=17.4, 10.7 Hz, 1H), 10.80 (br s, 1H).

後処理

  1. stirringAfter stirring at room temperature for 30 min
  2. extractionthe aqueous layer was extracted with dichloromethane (2×)
  3. filtrationfiltered through a phase separator
  4. customthe volatiles were removed in vacuo
  5. customThe residue was purified by silica gel chromatography
  6. washeluted with a continuous gradient of iso-hexanes/ethyl acetate 1:0 to 4:1

出典と根拠

ORDレコード
ord-dd8f1c8e05a44ecc9d741e2009b8cd10
出典データセット
uspto-grants-2015_09
特許番号
US09145441B2

反応ノート

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