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

Reaction equation

HRID 1628101 reaction equation
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]

Participants

8

Reactant 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, compound

Product 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)ethylcarbamateYield 45%

Reagents, catalysts & solvents 3

HCID 2723924Mercury bis(trifluoroacetate)CatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

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)+.

Workup

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

Sources & evidence

ORD record
ord-5d002257b52e4a059c6d6de3211b1b80
Source dataset
uspto-grants-2014_07
Patent number
US08785639B2

Linked notes

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