Piperidine → HCID 66599464、化合物

HRID 2410854ノート

反応式

HRID 2410854 の反応式
[CH2:1]([N:8]1[C:16]2[CH:15]=[C:14]([O:17][CH3:18])[CH:13]=[CH:12][C:11]=2[C:10]2[N:19]=[C:20](Br)[CH:21]=[C:22]([C:23]([O:25][CH3:26])=[O:24])[C:9]1=2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC1(C)C2C=CC=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=2OC2C1=CC=CC=2P(C1C=CC=CC=1)C1C=CC=CC=1.C([O-])([O-])=O.[Cs+].[Cs+].[NH:76]1[CH2:81][CH2:80][CH2:79][CH2:78][CH2:77]1>CCOC(C)=O.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.C(Cl)(Cl)Cl.[Pd].[Pd].O1CCOCC1>[CH2:1]([N:8]1[C:16]2[CH:15]=[C:14]([O:17][CH3:18])[CH:13]=[CH:12][C:11]=2[C:10]2[N:19]=[C:20]([N:76]3[CH2:81][CH2:80][CH2:79][CH2:78][CH2:77]3)[CH:21]=[C:22]([C:23]([O:25][CH3:26])=[O:24])[C:9]1=2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

8

反応物 4

HCID 8082PiperidineHCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 86663064HCID 86663064、化合物

生成物 1

HCID 66599464HCID 66599464、化合物収率 57.1%

試薬・触媒・溶媒 3

HCID 11029508Palladium, tris[mu-[(1,2-eta:4,5-eta)-(1E,4E)-1,5-diphenyl-1,4-pentadien-3-one]]di-, compd. with trichloromethane (1:1)触媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

A vial containing a mixture of methyl 5-benzyl-2-bromo-7-methoxy-5H-pyrido[3,2-b]indole-4-carboxylate (90 mg, 0.21 mmol), 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (18 mg, 0.032 mmol), tris(dibenzylideneacetone)dipalladium-chloroform adduct (11 mg, 11 μmol), Cs2CO3 (56 mg, 0.53 mmol) was flushed with nitrogen. Dioxane (1 mL) and piperidine (0.042 mL, 0.42 mmol) was added and the vial was sealed and heated at 100° C. overnight. This was then diluted with EtOAc, washed with water and brine, and dried over Na2SO4. Removal of the solvent followed by radial silica gel chromatography (step gradient elution with DCM containing 0 to 2% MeOH) afforded methyl 5-benzyl-7-methoxy-2-(piperidin-1-yl)-5H-pyrido[3,2-b]indole-4-carboxylate (51 mg, 0.12 mmol, 56% yield) as a solid. MS (ESI) m/z 430.2 (M+H). 1H NMR (500 MHz, chloroform-d) δ ppm 8.15 (1H, d, J=8.55 Hz), 7.25 (1H, s), 7.15-7.21 (2H, m), 6.89-6.94 (3H, m), 6.87 (1H, dd, J=8.55, 2.14 Hz), 6.78 (1H, d, J=2.14 Hz), 5.59 (2H, s), 3.84 (3H, s), 3.66 (3H, s), 3.53-3.61 (4H, m), 1.68-1.76 (4H, m), 1.61-1.68 (2H, m).

後処理

  1. additionA vial containing
  2. customwas flushed with nitrogen
  3. customthe vial was sealed
  4. washwashed with water and brine
  5. dry with materialdried over Na2SO4
  6. customRemoval of the solvent
  7. washfollowed by radial silica gel chromatography (step gradient elution with DCM containing 0 to 2% MeOH)

出典と根拠

ORDレコード
ord-84ba0ce988d445808cd58e3a796afc08
出典データセット
uspto-grants-2014_08
特許番号
US08815840B2

反応ノート

読み込み中…