2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → (9H-fluoren-9-yl)methyl 2-((3-(4-(2-hydroxypropan-2-yl)phenyl)-6-tosyl-6H-imidazo[1,5-a]pyrrolo[2,3-e]pyrazin-1-yl)methoxy)ethylcarbamate

HRID 1628101

反応式

HRID 1628101 の反応式
COC1C=CC(C[O:8][C:9]([C:12]2[CH:17]=[CH:16][C:15]([C:18]3[N:19]=[C:20]([CH2:40][O:41][CH2:42][CH2:43][NH:44][C:45](=[O:61])[O:46][CH2:47][CH:48]4[C:60]5[CH:59]=[CH:58][CH:57]=[CH:56][C:55]=5[C:54]5[C:49]4=[CH:50][CH:51]=[CH:52][CH:53]=5)[N:21]4[C:26]5[CH:27]=[CH:28][N:29]([S:30]([C:33]6[CH:39]=[CH:38][C:36]([CH3:37])=[CH:35][CH:34]=6)(=[O:32])=[O:31])[C:25]=5[N:24]=[CH:23][C:22]=34)=[CH:14][CH:13]=2)([CH3:11])[CH3:10])=CC=1.COC1C=CC(COC(C2C=CC([Mg]Br)=CC=2)(C)C)=CC=1.C1C2C(COC(NCCOCC(O)=O)=O)C3C(=CC=CC=3)C=2C=CC=1.C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>C(Cl)Cl.FC(F)(F)C([O-])=O.[Hg+2].FC(F)(F)C([O-])=O.O>[OH:8][C:9]([C:12]1[CH:13]=[CH:14][C:15]([C:18]2[N:19]=[C:20]([CH2:40][O:41][CH2:42][CH2:43][NH:44][C:45](=[O:61])[O:46][CH2:47][CH:48]3[C:49]4[CH:50]=[CH:51][CH:52]=[CH:53][C:54]=4[C:55]4[C:60]3=[CH:59][CH:58]=[CH:57][CH:56]=4)[N:21]3[C:26]4[CH:27]=[CH:28][N:29]([S:30]([C:33]5[CH:34]=[CH:35][C:36]([CH3:37])=[CH:38][CH:39]=5)(=[O:32])=[O:31])[C:25]=4[N:24]=[CH:23][C:22]=23)=[CH:16][CH:17]=1)([CH3:10])[CH3:11]

参加物

8

反応物 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 455991832-(2-((((9H-fluoren-9-yl)methoxy)carbonyl)amino)ethoxy)acetic acidHCID 67362121(9H-fluoren-9-yl)methyl 2-((3-(4-(2-(4-methoxybenzyloxy)propan-2-yl)phenyl)-6-tosyl-6H-imidazo[1,5-a]pyrrolo[2,3-e]pyrazin-1-yl)methoxy)ethylcarbamateHCID 178491445HCID 178491445、化合物

生成物 1

HCID 67216957(9H-fluoren-9-yl)methyl 2-((3-(4-(2-hydroxypropan-2-yl)phenyl)-6-tosyl-6H-imidazo[1,5-a]pyrrolo[2,3-e]pyrazin-1-yl)methoxy)ethylcarbamate収率 45%

試薬・触媒・溶媒 3

HCID 2723924Mercury bis(trifluoroacetate)触媒HCID 962Water溶媒HCID 6344Dichloromethane溶媒

実験手順

To a solution of (9H-fluoren-9-yl)methyl 2-((3-(4-(2-(4-methoxybenzyloxy)propan-2-yl)phenyl)-6-tosyl-6H-imidazo[1,5-a]pyrrolo[2,3-e]pyrazin-1-yl)methoxy)ethylcarbamate (0.077 g, 0.089 mmol, prepared using AF from Example #2, Step B cyano intermediate with ((4-(2-(4-methoxybenzyloxy)propan-2-yl)phenyl)magnesium bromide [NOVEL], AG, J.1 with 2-(2-(((9H-fluoren-9-yl)methoxy)carbonylamino)ethoxy)acetic acid [Chem Impex] and L.1 with mercury(II) trifluoroacetate) in DCM (0.94 mL) and Water (0.05 mL) was added DDQ (0.030 gg, 0.134 mmol). The mixture was stirred at rt for about 45 min. The mixture was directly purified by flash chromatography (12 g silica gel column, 35 to 100% EtOAc/heptane) to give (9H-fluoren-9-yl)methyl 2-((3-(4-(2-hydroxypropan-2-yl)phenyl)-6-tosyl-6H-imidazo[1,5-a]pyrrolo[2,3-e]pyrazin-1-yl)methoxy)ethylcarbamate (0.03 g, 45%): LC/MS (Table 2, Method b) Rt=2.90 min.; MS m/z: 742 (M+H)+.

後処理

  1. customThe mixture was directly purified by flash chromatography (12 g silica gel column, 35 to 100% EtOAc/heptane)

出典と根拠

ORDレコード
ord-5d002257b52e4a059c6d6de3211b1b80
出典データセット
uspto-grants-2014_07
特許番号
US08785639B2

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