Triphenylphosphine → methyl N-[[2-chloro-5-[2-(trimethylsilyl)ethynyl]phenyl]methyl]-carbamate

HRID 70246Notes

Reaction equation

HRID 70246 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][C:3]=1[CH2:9][NH:10][C:11](=[O:14])[O:12][CH3:13].[C:15]([Si:17]([CH3:20])([CH3:19])[CH3:18])#[CH:16].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1.C(N(CC)CC)C.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>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:16]#[C:15][Si:17]([CH3:20])([CH3:19])[CH3:18])=[CH:4][C:3]=1[CH2:9][NH:10][C:11](=[O:14])[O:12][CH3:13]

Participants

8

Reactant 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 66789912Methyl [(2-chloro-5-iodo-phenyl)methyl]carbamate2×

Product 1

HCID 66789132methyl N-[[2-chloro-5-[2-(trimethylsilyl)ethynyl]phenyl]methyl]-carbamate

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

A mixture methyl [(2-chloro-5-iodo-phenyl)methyl]carbamate (i.e. the product of Step B) (3.0 g, 9.2 mmol), ethynyltrimethylsilane (1.94 mL, 13.8 mmol), bis(triphenylphosphine)palladium(II) dichloride (0.032 g, 0.05 mmol), copper(I) iodide (0.018 g, 0.09 mmol), triphenylphosphine (0.024 g, 0.09 mmol) in tetrahydrofuran (18 mL) and triethylamine (18 mL) was stirred at room temperature for 30 minutes. The reaction mixture was concentrated onto silica gel (7 g) and then purified by medium pressure liquid chromatography (0 to 25% gradient of ethyl acetate in hexanes as eluant) to provide the title compound as an oil (1.37 g).

Workup

  1. concentrationThe reaction mixture was concentrated onto silica gel (7 g)
  2. custompurified by medium pressure liquid chromatography (0 to 25% gradient of ethyl acetate in hexanes as eluant)

Sources & evidence

ORD record
ord-86ac1409089b4cf7979e75fcccca5945
Source dataset
uspto-grants-2014_09
Patent number
US08822521B2

Reaction notes

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