Tris(1,1-dimethylethyl)phosphine → Methyl (3-(5-acetyl-2-methoxypyridin-3-yl)prop-2-yn-1-yl)carbamate

HRID 922426Notes

Reaction equation

HRID 922426 reaction equation
C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.Br[C:15]1[CH:16]=[C:17]([C:23](=[O:25])[CH3:24])[CH:18]=[N:19][C:20]=1[O:21][CH3:22].[CH2:26]([NH:29][C:30](=[O:33])[O:31][CH3:32])[C:27]#[CH:28]>CCCCCC.C(NC(C)C)(C)C.O1CCOCC1.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:23]([C:17]1[CH:16]=[C:15]([C:28]#[C:27][CH2:26][NH:29][C:30](=[O:33])[O:31][CH3:32])[C:20]([O:21][CH3:22])=[N:19][CH:18]=1)(=[O:25])[CH3:24]

Participants

9

Reactant 3

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 6917491methyl N-(prop-2-yn-1-yl)carbamateHCID 838940271-(5-Bromo-6-methoxypyridin-3-yl)ethan-1-one

Product 1

HCID 89939692Methyl (3-(5-acetyl-2-methoxypyridin-3-yl)prop-2-yn-1-yl)carbamateYield 71.7%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 7912DiisopropylamineSolventHCID 8058HexaneSolventHCID 312751,4-DioxaneSolvent2×

Procedure

Bis(benzonitrile)dichloropalladium (II) (12 mg) and copper (I) iodide (3.8 mg) were added to 1,4-dioxane (1 mL) under argon, and then thereto were added a solution of 10% tri-t-butylphosphine in hexane (179 μL), diisopropylamine (168 μL), 1-(5-bromo-6-methoxypyridin-3-yl)ethanone (230 mg) and a solution of methyl prop-2-yn-1-ylcarbamate (149 mg) in 1,4-dioxane (1 mL). The mixture was stirred at room temperature for 5 hours. The reaction solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate=3/1→1/3) to give methyl [3-(5-acetyl-2-methoxypyridin-3-yl)prop-2-yn-1-yl]carbamate [Ex(296-2)] (188 mg) as a pale yellow powder.

Workup

  1. concentrationThe reaction solution was concentrated under reduced pressure
  2. customthe resulting residue was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate=3/1→1/3)

Sources & evidence

ORD record
ord-87e3b48416a14021a631eb43c8bdc0df
Source dataset
uspto-grants-2016_03
Patent number
US09278944B2

Reaction notes

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