Triethylamine → (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-isocyanato-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-one

HRID 1400972ノート

反応式

HRID 1400972 の反応式
[CH3:1][C@:2]12[C@@:19]3([CH3:20])[C@@H:10]([C@:11]4([CH3:24])[C@@H:16]([CH2:17][CH2:18]3)[C:15]([CH3:22])([CH3:21])[C:14](=[O:23])[CH2:13][CH2:12]4)[CH2:9][CH2:8][C@@H:7]1[C@H:6]1[C@H:25]([C:28]([CH3:30])=[CH2:29])[CH2:26]C[C@]1(C(O)=O)[CH2:4][CH2:3]2.C([N:36]([CH2:39]C)[CH2:37][CH3:38])C.P(N=[N+]=[N-])(=O)(OC1C=CC=CC=1)[O:42]C1C=CC=CC=1>O1CCOCC1>[N:36]([C@:37]12[CH2:38][CH2:26][C@@H:25]([C:28]([CH3:30])=[CH2:29])[C@@H:6]1[C@@H:7]1[C@@:2]([CH3:1])([CH2:3][CH2:4]2)[C@@:19]2([CH3:20])[C@@H:10]([C@:11]3([CH3:24])[C@@H:16]([CH2:17][CH2:18]2)[C:15]([CH3:21])([CH3:22])[C:14](=[O:23])[CH2:13][CH2:12]3)[CH2:9][CH2:8]1)=[C:39]=[O:42]

参加物

5

反応物 3

HCID 8471TriethylamineHCID 122844(+)-Betulonic acidHCID 123414Diphenylphosphoryl azide

生成物 1

HCID 25426274(1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-isocyanato-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-one収率 63.2%

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒

実験手順

To a solution of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-9-oxo-1-(prop-1-en-2-yl)icosahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (16.41 g, 36.1 mmol) in 1,4-dioxane (200 mL) was added triethylamine (15.09 mL, 108 mmol) and diphenyl phosphorazidate (11.67 mL, 54.2 mmol). The mixture was heated to reflux for 18.5 h, then was cooled to rt and concentrated under reduced pressure. The residue was split into two portions and was purified using a 0-15% ethyl acetate in hexanes gradient and a Thomson 240 g silica gel column to purify each portion. The fractions containing the expected product were combined and concentrated under reduced pressure to give (1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-3a-isocyanato-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)octadecahydro-1H-cyclopenta[a]chrysen-9(5bH)-one (10.3 g, 22.80 mmol, 63.2% yield) as an off-white foam. 1H NMR (400 MHz, chloroform-d) δ=4.75 (d, J=2.0 Hz, 1H), 4.66-4.63 (m, 1H), 2.60-2.36 (m, 4H), 2.17-2.04 (m, 1H), 1.69 (s, 3H), 1.10 (s, 3H), 1.08 (s, 3H), 1.04 (s, 3H), 0.95 (s, 6H), 2.01-0.71 (m, 20H).

後処理

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 18.5 h
  3. concentrationconcentrated under reduced pressure
  4. customThe residue was split into two portions
  5. customwas purified
  6. customa Thomson 240 g silica gel column to purify each portion
  7. additionThe fractions containing the expected product
  8. concentrationconcentrated under reduced pressure

出典と根拠

ORDレコード
ord-81dc8f31d1414222984513c56e564f3b
出典データセット
uspto-grants-2014_12
特許番号
US08906889B2

反応ノート

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