Triphenylphosphine → (1S,4R)-4-[2-Chloro-6-(2,2-diphenyl-ethylamino)-purin-9-yl]-cyclopent-2-enol

HRID 1697001ノート

反応式

HRID 1697001 の反応式
[Cl:1][C:2]1[N:10]=[C:9]2[C:5]([N:6]=[CH:7][NH:8]2)=[C:4]([NH:11][CH2:12][CH:13]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[N:3]=1.[H-].[Na+].CC([O:31][C@H:32]1[CH:36]=[CH:35][C@@H:34](O)[CH2:33]1)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:1][C:2]1[N:10]=[C:9]2[C:5]([N:6]=[CH:7][N:8]2[C@@H:35]2[CH2:36][C@H:32]([OH:31])[CH:33]=[CH:34]2)=[C:4]([NH:11][CH2:12][CH:13]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[N:3]=1

参加物

6

反応物 4

HCID 11776TriphenylphosphineHCID 24758Sodium hydrideHCID 10154103rac-(1R,4S)-4-hydroxycyclopent-2-en-1-yl acetateHCID 178478404HCID 178478404、化合物

生成物 1

HCID 86622638(1S,4R)-4-[2-Chloro-6-(2,2-diphenyl-ethylamino)-purin-9-yl]-cyclopent-2-enol

試薬・触媒・溶媒 1

HCID 178418397HCID 178418397、化合物触媒

実験手順

(2-Chloro-9H-purin-6-yl)-(2,2-diphenyl-ethyl)-amine (12.92 g, 36.97 mmol) is placed in an oven-dried flask under an atmosphere of argon. Dry deoxygenated THF (100 ml) and dry DMSO (2 ml) are added and the suspension is cooled on an ice-bath. Sodium hydride 95% (0.89 g, 36.97 mmol) is then slowly added and the solution is stirred at room temperature for 30 minutes. (1S,4R)-cis 4-Acetoxy-2-cyclopenten-1-ol (5.00 g. 35.20 mmol) and triphenylphosphine (1.38 g, 5.28 mmol) are placed in an oven-dried flask under an atmosphere of argon. Dry deoxygenated THF (50 ml) is added. This solution is added to the anion solution. Tetrakis(triphenylphosphine)palladium(0) (2.03 g, 1.76 mmol) is added and the reaction mixture is stirred at 50° C. The reaction is shown to be complete by LCMS after 3 hours. The reaction mixture is allowed to cool and the solvent is removed in vacuo. The residue is taken up in dichloromethane (50 ml) and poured into vigorously stirring diethyl ether (300 ml). The precipitate is filtered off, the filtrate is taken and the solvent is removed in vacuo to give the title compound. 1H nmr (CDCl3, 400 MHz); 7.65(m, 1H), 7.35-7.15(m, 10H), 6.35(m, 1H), 5.90(m, 1H), 5.80(m, 1H), 5.50(m, 1H), 5.25(d, 1H), 4.85(t, 1H), 4.35(t, 1H), 4.25(m, 2H), 2.95(m, 1H), 2.15(d, 1H), MS (ES+) m/e 432 (MH+).

後処理

  1. customDry
  2. customdeoxygenated THF (100 ml) and dry DMSO (2 ml)
  3. additionare added
  4. temperaturethe suspension is cooled on an ice-bath
  5. customDry
  6. customdeoxygenated THF (50 ml)
  7. additionis added
  8. additionThis solution is added to the anion solution
  9. stirringthe reaction mixture is stirred at 50° C
  10. waitto be complete by LCMS after 3 hours
  11. temperatureto cool
  12. customthe solvent is removed in vacuo
  13. additionpoured into vigorously stirring diethyl ether (300 ml)
  14. filtrationThe precipitate is filtered off
  15. customthe solvent is removed in vacuo

出典と根拠

ORDレコード
ord-f84085c09a8e47f2ac0a600333ac1fe1
出典データセット
uspto-grants-2012_04
特許番号
US08163754B2

反応ノート

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