N,N'-Dimethylethylenediamine → tert-butyl 4-(6-(6-chloro-1H-pyrazolo[4,3-c]pyridin-1-yl)pyridin-2-yl)-6-methoxy-6-methyl-1,4-diazepane-1-carboxylate

HRID 57985Notes

Reaction equation

HRID 57985 reaction equation
Br[C:2]1[N:7]=[C:6]([N:8]2[CH2:14][C:13]([O:16][CH3:17])([CH3:15])[CH2:12][N:11]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:10][CH2:9]2)[CH:5]=[CH:4][CH:3]=1.[Cl:25][C:26]1[N:31]=[CH:30][C:29]2[CH:32]=[N:33][NH:34][C:28]=2[CH:27]=1.CNCCNC.C([O-])([O-])=O.[K+].[K+]>O1CCOCC1.[Cu]I>[Cl:25][C:26]1[N:31]=[CH:30][C:29]2[CH:32]=[N:33][N:34]([C:2]3[N:7]=[C:6]([N:8]4[CH2:14][C:13]([O:16][CH3:17])([CH3:15])[CH2:12][N:11]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:10][CH2:9]4)[CH:5]=[CH:4][CH:3]=3)[C:28]=2[CH:27]=1

Participants

7

Reactant 4

HCID 8070N,N'-DimethylethylenediamineHCID 11430Potassium CarbonateHCID 569321096-Chloro-1H-pyrazolo(4,3-c)pyridineHCID 86707169Tert-butyl 4-(6-bromopyridin-2-yl)-6-methoxy-6-methyl-1,4-diazepane-1-carboxylate

Product 1

HCID 86707168tert-butyl 4-(6-(6-chloro-1H-pyrazolo[4,3-c]pyridin-1-yl)pyridin-2-yl)-6-methoxy-6-methyl-1,4-diazepane-1-carboxylateYield 71%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

To a mixture of tert-butyl 4-(6-bromopyridin-2-yl)-6-methoxy-6-methyl-1,4-diazepane-1-carboxylate (530 mg, 1.33 mmol) and 6-chloro-1H-pyrazolo[4,3-c]pyridine (203 mg, 1.33 mmol) in 1,4-dioxane (30 mL) was added CuI (101 mg, 0.53 mmol), N1,N2-dimethylethane-1,2-diamine (94 mg, 1.06 mmol), and K2CO3 (734 mg, 5.32 mmol). The mixture was heated at 100° C., which was monitored by LCMS. After completion of the reaction, it was concentrated under reduced pressure. The crude material was purified by silica gel chromatography using petroleum ether:EtOAc (3:1˜1:1) as eluting solvents to afford tert-butyl 4-(6-(6-chloro-1H-pyrazolo[4,3-c]pyridin-1-yl)pyridin-2-yl)-6-methoxy-6-methyl-1,4-diazepane-1-carboxylate as yellow solid (446 mg, 71%). MS (ESI) m/z: 473 [M+H]+.

Workup

  1. customAfter completion of the reaction, it
  2. concentrationwas concentrated under reduced pressure
  3. customThe crude material was purified by silica gel chromatography
  4. washas eluting solvents

Sources & evidence

ORD record
ord-b2b54dee3fc848fe8cbc37fa0a082e1f
Source dataset
uspto-grants-2016_09
Patent number
US09434725B2

Reaction notes

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