N,N'-Dimethylethylenediamine → (S,E)-tert-butyl 4-(4-(5,6-dichloro-1-oxo-3,4-dihydroisoquinolin-2(1H)-yl)styryl)-2,2-dimethyloxazolidine-3-carboxylate

HRID 1805244Notes

Reaction equation

HRID 1805244 reaction equation
[C:1]([O:5][C:6]([N:8]1[C@@H:12](/[CH:13]=[CH:14]/[C:15]2[CH:20]=[CH:19][C:18](I)=[CH:17][CH:16]=2)[CH2:11][O:10][C:9]1([CH3:23])[CH3:22])=[O:7])([CH3:4])([CH3:3])[CH3:2].[Cl:24][C:25]1[C:34]([Cl:35])=[CH:33][CH:32]=[C:31]2[C:26]=1[CH2:27][CH2:28][NH:29][C:30]2=[O:36].CNCCNC.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>C1(C)C=CC=CC=1.[Cu]I>[Cl:24][C:25]1[C:34]([Cl:35])=[CH:33][CH:32]=[C:31]2[C:26]=1[CH2:27][CH2:28][N:29]([C:18]1[CH:19]=[CH:20][C:15](/[CH:14]=[CH:13]/[C@H:12]3[CH2:11][O:10][C:9]([CH3:23])([CH3:22])[N:8]3[C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])=[CH:16][CH:17]=1)[C:30]2=[O:36]

Participants

7

Reactant 4

HCID 8070N,N'-DimethylethylenediamineHCID 62657Potassium Phosphate, TribasicHCID 125950965,6-Dichloro-1,2,3,4-tetrahydroisoquinolin-1-oneHCID 67151621HCID 67151621, compound

Product 1

HCID 67151848(S,E)-tert-butyl 4-(4-(5,6-dichloro-1-oxo-3,4-dihydroisoquinolin-2(1H)-yl)styryl)-2,2-dimethyloxazolidine-3-carboxylateYield 61.1%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 1140TolueneSolvent

Conditions

Temperature
120 °C

Procedure

A stirred suspension of (S)-4-[(E)-2-(4-iodo-phenyl)-vinyl]-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester (300 mg, Example 3a), 5,6-dichloro-3,4-dihydro-2H-isoquinolin-1-one (204 mg), copper(I) iodide (13 mg), N,N′-dimethylethylenediamine (15 μl) and potassium phosphate (356 mg) in toluene (3 ml) in a sealed tube was heated at 120° C. overnight. The mixture was then cooled to room temperature and was purified by column chromatography (SiO2; gradient: heptane/EtOAc) to give (S,E)-tert-butyl 4-(4-(5,6-dichloro-1-oxo-3,4-dihydroisoquinolin-2(1H)-yl)styryl)-2,2-dimethyloxazolidine-3-carboxylate (221 mg, 61%) as a yellow amorphous solid. MS (ISP): 541.2 ([{37Cl35Cl}M+Na]+), 539.2 ([{35Cl}M+Na]+), 519.3 ([{37Cl35Cl}M+H]+), 517.2 ([{35Cl}M+H]+), 463.2 ([{37Cl35Cl}M+H—C4H8]+), 461.2 ([{35Cl}M+H—C4H8]+), 419.2 ([{37Cl35Cl}M+H—C4H8—CO2]+), 417.2 ([{35Cl}M+H—C4H8—CO2]+).

Workup

  1. temperatureThe mixture was then cooled to room temperature
  2. customwas purified by column chromatography (SiO2; gradient: heptane/EtOAc)

Sources & evidence

ORD record
ord-d20f9fad6c3a436fa5e645786fef879b
Source dataset
uspto-grants-2013_01
Patent number
US08354441B2

Reaction notes

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