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4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole → 6-(1H-pyrazol-4-yl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[4,3-c]pyridine

HRID 57979
Notes
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Reaction equation

HRID 57979 reaction equation
Cl[C:2]1[N:7]=[CH:6][C:5]2[CH:8]=[N:9][N:10]([CH2:11][O:12][CH2:13][CH2:14][Si:15]([CH3:18])([CH3:17])[CH3:16])[C:4]=2[CH:3]=1.CC1(C)C(C)(C)OB([C:27]2[CH:28]=[N:29][NH:30][CH:31]=2)O1>C([O-])([O-])=O.[Na+].[Na+].O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[NH:29]1[CH:28]=[C:27]([C:2]2[N:7]=[CH:6][C:5]3[CH:8]=[N:9][N:10]([CH2:11][O:12][CH2:13][CH2:14][Si:15]([CH3:18])([CH3:17])[CH3:16])[C:4]=3[CH:3]=2)[CH:31]=[N:30]1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 2

HCID 27740104-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazoleHCID 867070302-[(6-Chloropyrazolo[4,3-c]pyridin-1-yl)methoxy]ethyl-trimethyl-silane

Product 1

HCID 867071616-(1H-pyrazol-4-yl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[4,3-c]pyridineYield 46.2%

Reagents, catalysts & solvents 3

HCID 44119782Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)
Catalyst
HCID 10340Sodium CarbonateSolvent
HCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

A suspension of 6-chloro-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[4,3-c]pyridine (1.30 g, 4.6 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (1.16 g, 6 mmol), and Pd(dppf)Cl2 (437 mg, 0.6 mmol) in aq. Na2CO3 (2.0 M, 12 mL) and 1,4-dioxane (20 mL) was heated at 110° C. for 20 hours. The reaction mixture was concentrated under reduced pressure. The residue was purified by silica gel chromatography using ethyl acetate/heptanes 50% to 100% as eluting solvents to afford 6-(1H-pyrazol-4-yl)-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazolo[4,3-c]pyridine as a yellow oil (670 mg, 46%), and recovered 1 g of the starting material. MS (ESI) m/z: 316 [M+H]+.

Workup

  1. concentrationThe reaction mixture was concentrated under reduced pressure
  2. customThe residue was purified by silica gel chromatography
  3. washas eluting solvents

Sources & evidence

ORD record
ord-d08bd09121604b0c84895928fcefa6cc
Source dataset
uspto-grants-2016_09
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09434725B2

Reaction notes

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