N,N'-Dimethylethylenediamine → benzyl 1-oxo-2-(5-(pyridin-3-yl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[3,4-c]pyridin-3-yl)-2,8-diazaspiro[4.5]decane-8-carboxylate

HRID 1775096Notes

Reaction equation

HRID 1775096 reaction equation
I[C:2]1[C:10]2[C:5](=[CH:6][N:7]=[C:8]([C:11]3[CH:12]=[N:13][CH:14]=[CH:15][CH:16]=3)[CH:9]=2)[N:4]([CH2:17][O:18][CH2:19][CH2:20][Si:21]([CH3:24])([CH3:23])[CH3:22])[N:3]=1.[O:25]=[C:26]1[C:30]2([CH2:35][CH2:34][N:33]([C:36]([O:38][CH2:39][C:40]3[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=3)=[O:37])[CH2:32][CH2:31]2)[CH2:29][CH2:28][NH:27]1.CNCCNC.C(=O)([O-])[O-].[Cs+].[Cs+].O1CCOCC1>[Cu]I>[O:25]=[C:26]1[C:30]2([CH2:35][CH2:34][N:33]([C:36]([O:38][CH2:39][C:40]3[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=3)=[O:37])[CH2:32][CH2:31]2)[CH2:29][CH2:28][N:27]1[C:2]1[C:10]2[C:5](=[CH:6][N:7]=[C:8]([C:11]3[CH:12]=[N:13][CH:14]=[CH:15][CH:16]=3)[CH:9]=2)[N:4]([CH2:17][O:18][CH2:19][CH2:20][Si:21]([CH3:24])([CH3:23])[CH3:22])[N:3]=1

Participants

7

Reactant 5

HCID 8070N,N'-DimethylethylenediamineHCID 10796Cesium carbonateHCID 312751,4-DioxaneHCID 71253586HCID 71253586, compoundHCID 71253694Benzyl 1-oxo-2,8-diazaspiro[4.5]decane-8-carboxylate

Product 1

HCID 71253852benzyl 1-oxo-2-(5-(pyridin-3-yl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[3,4-c]pyridin-3-yl)-2,8-diazaspiro[4.5]decane-8-carboxylateYield 52.7%

Reagents, catalysts & solvents 1

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst

Conditions

Temperature
75 °C

Procedure

A solution containing 3-iodo-5-(pyridin-3-yl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[3,4-c]pyridine (0.196 g, 0.434 mmol), benzyl 1-oxo-2,8-diazaspiro[4.5]decane-8-carboxylate (0.250 g, 0.867 mmol), N,N′-Dimethylethylenediamine (0.103 mL, 0.954 mmol), Copper(I) iodide (0.0908 g, 0.477 mmol) and Cesium Carbonate (0.311 g, 0.954 mmol) in 1,4-Dioxane (7.08 mL, 90.7 mmol) was stirred at 75° C. for 2 h. The reaction was filtered thru celite and concentrated. The crude product purified by Isco column (EtOAc/Hep eluted at 50% EtOAc) to give benzyl 1-oxo-2-(5-(pyridin-3-yl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[3,4-c]pyridin-3-yl)-2,8-diazaspiro[4.5]decane-8-carboxylate (140 mg, 52.7% yield). ESI MS m/z=613.1 (M+1).

Workup

  1. filtrationThe reaction was filtered thru celite
  2. concentrationconcentrated
  3. customThe crude product purified by Isco column (EtOAc/Hep eluted at 50% EtOAc)

Sources & evidence

ORD record
ord-86f70e1183554217b285aa837bcfcaf2
Source dataset
uspto-grants-2016_02
Patent number
US09260425B2

Reaction notes

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