Stannane, tributyl(1-ethoxyethenyl)- → 3-Chloro-6-(1-ethoxy-vinyl)-isoquinoline

HRID 1895777Notes

Reaction equation

HRID 1895777 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[N:7][C:6]([Cl:12])=[CH:5]2.C([Sn](CCCC)(CCCC)[C:18]([O:20][CH2:21][CH3:22])=[CH2:19])CCC>C1(C)C=CC=CC=1.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>[Cl:12][C:6]1[N:7]=[CH:8][C:9]2[C:4]([CH:5]=1)=[CH:3][C:2]([C:18]([O:20][CH2:21][CH3:22])=[CH2:19])=[CH:11][CH:10]=2

Participants

5

Reactant 2

HCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 226075306-Bromo-3-chloroisoquinoline

Product 1

HCID 866758623-Chloro-6-(1-ethoxy-vinyl)-isoquinolineYield 103.1%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
50 °C

Procedure

A solution of 6-bromo-3-chloro-isoquinoline (972 mg, 4 mmol) and tributyl-(1-ethoxy-vinyl)-stannane (2.5 g, 2.5 mL, 7 mmol) in toluene (12 mL) was degassed with nitrogen for 30 minutes. Bis(triphenylphosphine)palladium(II) dichloride (280 mg, 0.4 mmol) was added and the reaction mixture was heated at 50° C. for 18 h. The reaction mixture was cooled to room temperature and the mixture was purified by silica gel chromatography using a gradient of iso-hexanes/ethyl acetate 20:1 to 10:1 to afford the title compound (964 mg). 1H NMR (300 MHz, CDCl3) δ1.51 (t, J=7.0 Hz, 3H), 4.01 (q, J=7.0 Hz, 2H), 4.45 (d, J=2.8 Hz, 1H), 4.90 (d, J=2.8 Hz, 1H), 7.76 (s, 1H), 7.85-7.97 (m, 2H), 8.04 (s, 1H), 0.94 (s, 1H). LCMS (m/z) 234/236 [M+H], Tr=5.40 min.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. customthe mixture was purified by silica gel chromatography

Sources & evidence

ORD record
ord-695dfdd407d04ad89f07a39f889a62b4
Source dataset
uspto-grants-2013_08
Patent number
US08513184B2

Reaction notes

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