Dichloromethane → Methyl (65)-2'-oxo-1'-{[2-(trimethylsilyl)ethoxy]methyl}-1',2',5,7-tetrahydrospiro[cyclopenta[b]pyridine-6,3'-pyrrolo[2,3-b]pyridine]-3-carboxylate

HRID 448204ノート

反応式

HRID 448204 の反応式
Br[C:2]1[CH:3]=[C:4]2[CH2:27][C:9]3([C:17]4[C:12](=[N:13][CH:14]=[CH:15][CH:16]=4)[N:11]([CH2:18][O:19][CH2:20][CH2:21][Si:22]([CH3:25])([CH3:24])[CH3:23])[C:10]3=[O:26])[CH2:8][C:5]2=[N:6][CH:7]=1.[CH2:28](Cl)Cl.[C:31]([O-:34])(=[O:33])C.[Na+].[C]=O>CO.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[O:26]=[C:10]1[N:11]([CH2:18][O:19][CH2:20][CH2:21][Si:22]([CH3:25])([CH3:24])[CH3:23])[C:12]2=[N:13][CH:14]=[CH:15][CH:16]=[C:17]2[C@@:9]21[CH2:8][C:5]1=[N:6][CH:7]=[C:2]([C:31]([O:34][CH3:28])=[O:33])[CH:3]=[C:4]1[CH2:27]2

参加物

7

反応物 4

HCID 6344DichloromethaneHCID 517045Sodium AcetateHCID 68749705HCID 68749705、化合物HCID 178418416HCID 178418416、化合物

生成物 1

HCID 86665189Methyl (65)-2'-oxo-1'-{[2-(trimethylsilyl)ethoxy]methyl}-1',2',5,7-tetrahydrospiro[cyclopenta[b]pyridine-6,3'-pyrrolo[2,3-b]pyridine]-3-carboxylate

試薬・触媒・溶媒 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 887Methanol溶媒

反応条件

温度
85 °C

実験手順

A mixture of 3-bromo-1′-{[2-(trimethylsilyl)ethoxy]methyl}-5,7-dihydrospiro[cyclopenta[b]pyridine-6,3′-pyrrolo[2,3-b]pyridine]-2′(1′H)-one (22.0 g, 49.3 mmol), PdCl2(dppf).CH2Cl2 (2.012 g, 2.46 mmol), and sodium acetate (8.1 g, 99 mmol) in in methanol (150 mL) was pressurized to 300 psi of carbon monoxide and then heated at 85° C. for 72 h. The reaction mixture was allowed to cool then concentrated. The residue was purified via silica gel chromatography (heptane initially, grading to 100% EtOAc) to give the title compound as a racemic mixture. MS: m/z=426.1 (M+1). Resolution of the enantiomers by supercritical fluid chromatography (SFC) using a ChiralPak® AD-H column and eluting with 40% ethanol in CO2 (0.05% diethylamine as modifier) provided the title compound as the second enantiomer to elute.

後処理

  1. temperatureto cool
  2. concentrationthen concentrated
  3. customThe residue was purified via silica gel chromatography (heptane initially

出典と根拠

ORDレコード
ord-d6bd5906ab3542c8b4efffadcaf1cfbb
出典データセット
uspto-grants-2013_07
特許番号
US08481556B2

反応ノート

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