Phenylboronic Acid → (7R,8R,9R)-10-acetyl-3,9-diphenyl-7-(2-methoxyethoxy)-2-methyl-8-pivaloyloxy-7,8,9,10-tetrahydroimidazo[1,2-h][1,7]naphthyridine

HRID 723408ノート

反応式

HRID 723408 の反応式
[C:1]([N:4]1[C:13]2[C:12]3=[N:14][C:15]([CH3:18])=[C:16](Br)[N:11]3[CH:10]=[CH:9][C:8]=2[C@@H:7]([O:19][CH2:20][CH2:21][O:22][CH3:23])[C@H:6]([O:24][C:25](=[O:30])[C:26]([CH3:29])([CH3:28])[CH3:27])[C@H:5]1[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)(=[O:3])[CH3:2].[C:37]1(B(O)O)[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1.[F-].[K+].P(C(C)(C)C)(C(C)(C)C)C(C)(C)C>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1COCC1>[C:1]([N:4]1[C:13]2[C:12]3=[N:14][C:15]([CH3:18])=[C:16]([C:37]4[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=4)[N:11]3[CH:10]=[CH:9][C:8]=2[C@@H:7]([O:19][CH2:20][CH2:21][O:22][CH3:23])[C@H:6]([O:24][C:25](=[O:30])[C:26]([CH3:29])([CH3:28])[CH3:27])[C@H:5]1[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)(=[O:3])[CH3:2]

参加物

7

反応物 4

HCID 66827Phenylboronic AcidHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 522689Potassium FluorideHCID 69586421HCID 69586421、化合物

生成物 1

HCID 69586312(7R,8R,9R)-10-acetyl-3,9-diphenyl-7-(2-methoxyethoxy)-2-methyl-8-pivaloyloxy-7,8,9,10-tetrahydroimidazo[1,2-h][1,7]naphthyridine

試薬・触媒・溶媒 2

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
25 °C

実験手順

2.61 g (4.67 mmol) (7R,8R,9R)-10-acetyl-3-bromo-7-(2-methoxyethoxy)-2-methyl-9-phenyl-8-pivaloyloxy-7.8.9.10-tetrahydroimidazo[1.2-h][1.7]naphthyridine, 0.63 g (5.14 mmol) phenylboronic acid, 0.89 g (15.4 mmol) KF (spray-dried), 0.14 g (0.15 mmol) Pd2(dba)3, 0.07g (0.36 mmol/10wt % solution in hexane)P(t-Bu)3 and THF (30 ml) are added to a Schlenk tube under argon. Afterwards the Schlenk tube is evacuated and refilled with argon in a freeze-pump-thaw cycles technique three times. The reaction mixture is stirred under argon for 2 d at 25° C. Subsequently the reaction is diluted by adding of ethyl acetate and then filtrated through silica gel. The concentrated crude product is purified by column chromatography (diethyl ether/petrol ether: 6/4) to give 1.80 g (3.24 mmol/70%) of the title compound as an amorphous colourless solid. 1H-NMR (200 MHz, [D6] DMSO): δ=1.20 (s, 9H), 2.20(s, 3H), 2.43(s, 3H), 3.30 (s, 3H), 3.40–3.57(m, 2H), 3.88 (t, 2H), 4.64 (d, 1H), 5.35 (t, 1H), 5.83(d, 1H), 7.00(d, 1H), 7.10–7.30(m, 5H), 7.41–7.68 (m, 5H), 8.24(d, 1H).

後処理

  1. customAfterwards the Schlenk tube is evacuated
  2. additionrefilled with argon in a freeze-pump-thaw cycles technique three times
  3. additionSubsequently the reaction is diluted
  4. additionby adding of ethyl acetate
  5. filtrationfiltrated through silica gel
  6. concentrationThe concentrated crude product
  7. customis purified by column chromatography (diethyl ether/petrol ether: 6/4)

出典と根拠

ORDレコード
ord-c428b6b6c48347bc98f348eb0deb5cc7
出典データセット
uspto-grants-2006_11
特許番号
US07141567B2

反応ノート

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