1-Penten-3-one → HCID 11323666、化合物

HRID 735281ノート

反応式

HRID 735281 の反応式
Cl(O)(=O)(=O)=O.[CH:6]([C:8]([CH2:10][CH3:11])=[O:9])=[CH2:7].C([C@@H]1N[C@H](C2OC(C)=CC=2)N(C)C1=O)C1C=CC=CC=1.[CH2:32]([O:39][C:40](=[O:46])[NH:41][CH:42]=[CH:43][CH:44]=[CH2:45])[C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1>C(O)C.CCOCC>[C:8]([C@H:10]1[C@@H:42]([NH:41][C:40](=[O:46])[O:39][CH2:32][C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[CH:43]=[CH:44][CH2:45][CH2:11]1)(=[O:9])[CH2:6][CH3:7]

参加物

7

反応物 4

HCID 153941-Penten-3-oneHCID 24247Perchloric AcidHCID 329894HCID 329894、化合物HCID 11303220(2S,5S)-(-)-5-Benzyl-3-methyl-2-(5-methyl-2-furyl)-4-imidazolidinone

生成物 1

HCID 11323666HCID 11323666、化合物収率 91%

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒HCID 3283Diethyl Ether溶媒

反応条件

温度
-30 °C

実験手順

Concentrated (70% aqueous) perchloric acid (431 μL, 5.0 mmol) was added slowly to a stirring solution of ethyl vinyl ketone (2.49 mL, 25.0 mmol) and (2S, 5S)-5-benzyl-3-methyl-2-(5-methyl-furan-2-yl)-imidazolidin-4-one (1.35 g, 5.0 mmol) pre-chilled to −30° C. Then, buta-1,3-dienyl-carbamic acid benzyl ester (4.47g, 31.3 mmol) was added dropwise over 15 minutes as a solution in 12.5 mL of absolute ethanol. After stirring for 3.5 days, the reaction was diluted with ether (150 mL), washed successively with 1N HCl (50 mL), water (50 mL) and brine (25 mL). The organic layer was then dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo to afford a pale brown oil. Purification by silica gel (8:1 hexanes:ethyl acetate) afforded the title compound as a single diastereomer (as judged by HPLC analysis) in 91% yield (5.17g, 22.7 mmol) and 98% ee. The combined aqueous extracts were treated with solid K2CO3, extracted with 3×50 mL portions of CHCl3, dried over anhydrous Na2SO4 and concentrated in vacuo to afford a 91% recovery of (2S, 5S)-5-benzyl-3-methyl-2-(5-methyl-furan-2-yl)-imidazolidin-4-one (1.23 g, 4.55 mmol) after silica gel chromatography. IR (film) 3411, 3329, 3064, 3031, 2974, 2938, 2879, 2836, 1956, 1872, 1711, 1523, 1455, 1409, 1376, 1331, 1278, 1236, 1164, 1120, 1060, 1028, 988.9, 973.1, 775.6, 736.0, 697.9 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.33 (m, 5H, ArH), 5.82 (m, 1H, CH═CH), 5.70 (m, 1H, CH═CH), 5.04 (m, 3H, CH2Ph and NH), 4.63 (m, 1H, CHNH), 2.86 (ddd, J=10.2, 3.9, 3.9 Hz, 1H, CHCO), 2.70 (dq, J=18.0, 7.2 Hz, 1H, one of CH2CO), 2.43 (dq, J=17.7, 7.2 Hz, 1H, one of CH2CO), 2.10-1.65 (m, 4H, CH2CH2), 1.00 (dd, J=6.9, 6.9 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3) δ 212.0, 155.9, 136.6, 130.1, 128.7, 128.2, 128.1, 126.9, 67.0, 50.4, 46.9, 34.8, 24.2, 20.7, 8.0; HRMS (CI) exact mass calc'd for (C17H21NO3) requires m/z 287.1521, found m/z 287.1519. [α]D=+122.0 (c=1.0, CHCl3). Product ratios were determined by HPLC analysis (OD-H column, 3% ethanol in hexanes, 1 mL/min, 254 nm); (1S, 6R) endo isomer tr=12.5 min, and (1R, 6S) endo isomer tr=11.3 min, exo isomers tr=8.6, 9.2 min.

後処理

  1. washwashed successively with 1N HCl (50 mL), water (50 mL) and brine (25 mL)
  2. dry with materialThe organic layer was then dried over anhydrous magnesium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customto afford a pale brown oil
  6. customPurification by silica gel (8:1 hexanes:ethyl acetate)

出典と根拠

ORDレコード
ord-146198bcf3d04f4abccde464a83d6b15
出典データセット
uspto-grants-2009_09
特許番号
US07592463B2

反応ノート

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