Trimethylsilylacetylene → HCID 67540580, compound

HRID 1192299Notes

Reaction equation

HRID 1192299 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][N:11]([C:14]2[C:19]([NH2:20])=[C:18](Cl)[N:17]=[CH:16][N:15]=2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[Si:22]([C:26]#[CH:27])([CH3:25])([CH3:24])[CH3:23]>C1COCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][N:11]([C:14]2[C:19]([NH2:20])=[C:18]([C:27]#[C:26][Si:22]([CH3:25])([CH3:24])[CH3:23])[N:17]=[CH:16][N:15]=2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 71748362tert-Butyl 4-(5-amino-6-chloropyrimidin-4-yl)piperazine-1-carboxylate

Product 1

HCID 67540580HCID 67540580, compoundYield 25%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 4-(5-amino-6-chloropyrimidin-4-yl)-piperazine-1-carboxylic acid tert-butyl ester (1 g, 3.19 mmol) and TMS-acetylene (1.5 g, 15 mmol) in TEA (10 mL) and THF (30 mL) were added PdCl2(PPh3)2 (0.33 g, 0.47 mmol) and CuI (0.1 g, 0.53 mmol) under N2. The mixture was heated to 80° C. for 20 hours. The solvent was removed and the residue was subject to chromatography on silica gel to afford the product 4-(5-Amino-6-trimethylsilanylethynyl-pyrimidin-4-yl)-piperazine-1-carboxylic acid tert-butyl ester (0.3 g, 25%). 1H NMR (CDCl3, 400 Hz) δ 8.00 (s, 1H), 3.74 (s, 2H), 3.28-3.25 (m, 4H), 3.02-2.99 (m, 4H), 1.20 (s, 9H), 0.00 (s, 9H). MS (ESI+) [M+H]+ 376.

Workup

  1. customThe solvent was removed

Sources & evidence

ORD record
ord-dae2e50c0ffb4ef59be59ab309c7423b
Source dataset
uspto-grants-2014_03
Patent number
US08680114B2

Reaction notes

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