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

HRID 1496652Notes

Reaction equation

HRID 1496652 reaction equation
[CH3:1][O:2][C:3](=[O:14])[NH:4][CH2:5][C:6]1[CH:11]=[C:10](I)[CH:9]=[CH:8][C:7]=1[Cl: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:13][C:7]1[CH:8]=[CH:9][C:10]([C:16]#[C:15][Si:17]([CH3:20])([CH3:19])[CH3:18])=[CH:11][C:6]=1[CH2:5][NH:4][C:3](=[O:14])[O:2][CH3:1]

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-2e1fbe7e9df64bc880f247b6011844b0
Source dataset
uspto-grants-2015_12
Patent number
US09198433B2

Reaction notes

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