Hydrochloric Acid → (2S,6R,8aR)-2-amino-6-(7-tosyl-7H-pyrrolo[2,3-d]pyrimidin-4-ylamino)hexahydroindolizin-3(5H)-one

HRID 919634ノート

反応式

HRID 919634 の反応式
[O:1]=[C:2]1[N:10]2[C@H:5]([CH2:6][CH2:7][C@@H:8]([NH:11][C:12]3[C:13]4[CH:20]=[CH:19][N:18]([S:21]([C:24]5[CH:30]=[CH:29][C:27]([CH3:28])=[CH:26][CH:25]=5)(=[O:23])=[O:22])[C:14]=4[N:15]=[CH:16][N:17]=3)[CH2:9]2)[CH2:4][C@@H:3]1[NH:31]C(=O)OC(C)(C)C.Cl>CO.O1CCOCC1>[NH2:31][C@@H:3]1[C:2](=[O:1])[N:10]2[C@H:5]([CH2:6][CH2:7][C@@H:8]([NH:11][C:12]3[C:13]4[CH:20]=[CH:19][N:18]([S:21]([C:24]5[CH:25]=[CH:26][C:27]([CH3:28])=[CH:29][CH:30]=5)(=[O:23])=[O:22])[C:14]=4[N:15]=[CH:16][N:17]=3)[CH2:9]2)[CH2:4]1

参加物

5

反応物 2

HCID 313Hydrochloric AcidHCID 68070554tert-butyl (2S,6R,8aR)-3-oxo-6-(7-tosyl-7H-pyrrolo[2,3-d]pyrimidin-4-ylamino)-octahydroindolizin-2-ylcarbamate

生成物 1

HCID 68070553(2S,6R,8aR)-2-amino-6-(7-tosyl-7H-pyrrolo[2,3-d]pyrimidin-4-ylamino)hexahydroindolizin-3(5H)-one

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 312751,4-Dioxane溶媒

実験手順

A solution of tert-butyl (2S,6R,8aR)-3-oxo-6-(7-tosyl-7H-pyrrolo[2,3-d]pyrimidin-4-ylamino)-octahydroindolizin-2-ylcarbamate 127.4 (550 mg (1.02 mmole) in MeOH (21 mL) was treated with of 4 M HCl in 1,4-dioxane (4.0 mL (20.3 mmol) and stirred at room temperature for 23 hr. The mixture was concentrated to dryness, and the residue was dissolved in MeOH (20 ml) and treated with polymer-supported carbonate resin (1.2 g, 3.5 mmol/g). The suspension was stirred at room temperature for 1 hour. The resin was removed by filtration through a celite plug, and the filtrate was concentrated in vacuo to yield 414 mg of (2S,6R,8aR)-2-amino-6-(7-tosyl-7H-pyrrolo[2,3-d]pyrimidin-4-ylamino)hexahydroindolizin-3(5H)-one 127.5 as pale yellow solid that was used without further purification. 1H NMR (400 MHz, CHLOROFORM-d) δ 8.42 (s, 1H), 8.04 (d, J=8.3 Hz, 2H), 7.43 (d, J=4.0 Hz, 1H), 7.28 (d, J=8.8 Hz, 2H), 6.49 (d, J=3.8 Hz, 1H), 5.64-5.46 (m, 1H), 4.41 (br. s., 1H), 4.22 (d, J=14.1 Hz, 1H), 3.72-3.54 (m, 2H), 3.08 (dd, J=3.1, 13.9 Hz, 1H), 2.38 (s, 3H), 2.10 (ddd, 0.1=4.3, 8.7, 13.3 Hz, 1H), 2.04-1.91 (m, 1H), 1.90-1.61 (m, 4H), 1.47 (dd, J=2.9, 11.9 Hz, 1H); LCMS (ESI) m/z: 441.2 [M+H]+.

後処理

  1. concentrationThe mixture was concentrated to dryness
  2. dissolutionthe residue was dissolved in MeOH (20 ml)
  3. additiontreated with polymer-supported carbonate resin (1.2 g, 3.5 mmol/g)
  4. stirringThe suspension was stirred at room temperature for 1 hour
  5. customThe resin was removed by filtration through a celite plug
  6. concentrationthe filtrate was concentrated in vacuo

出典と根拠

ORDレコード
ord-09927fd486d24a39ac34a01efc1ab90c
出典データセット
uspto-grants-2016_03
特許番号
US09273028B2

反応ノート

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