6-(2,2-Dibromo-vinyl)-2-cyclopropyl-4,4-dimethyl-1,2,3,4-tetrahydroisoquinoline-6-carboxaldehyde → 2-Cyclopropyl-6-ethynyl-4,4-dimethyl-1,2,3,4-tetrahydroisoquinoline

HRID 24079Notes

Reaction equation

HRID 24079 reaction equation
Br[C:2](Br)=[CH:3][C:4]1(C=O)[CH:13]=[CH:12][C:11]2[CH2:10][N:9]([CH:14]3[CH2:16][CH2:15]3)[CH2:8][C:7]([CH3:18])([CH3:17])[C:6]=2[CH2:5]1.C([Li])CCC>O1CCCC1>[CH:14]1([N:9]2[CH2:8][C:7]([CH3:17])([CH3:18])[C:6]3[C:11](=[CH:12][CH:13]=[C:4]([C:3]#[CH:2])[CH:5]=3)[CH2:10]2)[CH2:16][CH2:15]1

Participants

4

Reactant 2

HCID 225688196-(2,2-Dibromo-vinyl)-2-cyclopropyl-4,4-dimethyl-1,2,3,4-tetrahydroisoquinoline-6-carboxaldehyde2×HCID 178418339Butyllithium

Product 1

HCID 225689952-Cyclopropyl-6-ethynyl-4,4-dimethyl-1,2,3,4-tetrahydroisoquinolineYield 94.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-20 °C

Procedure

A stirred, cooled (−78° C.) solution of 6-(2,2-dibromo-vinyl)-2-cyclopropyl-4,4-dimethyl-1,2,3,4-tetrahydroisoquinoline-6-carboxaldehyde (Intermediate 26, 0.1 8 g, 0.47 mmol) in tetrahydrofuran (2 mL) was treated with 1.6M solution of n-butyl lithium (0.6 mL, 0.96 mmol) under argon. The reaction mixture was allowed to warm to −20° C. over 1.5 h, quenched with saturated aqueous ammonium chloride solution and extracted with diethyl ether (×2). The combined organic phase was dried over anhydrous magnesium sulfate, filtered and evaporated in vacuo to afford the title compound as an oil (0.1 g, 94%).

Workup

  1. customquenched with saturated aqueous ammonium chloride solution
  2. extractionextracted with diethyl ether (×2)
  3. dry with materialThe combined organic phase was dried over anhydrous magnesium sulfate
  4. filtrationfiltered
  5. customevaporated in vacuo

Sources & evidence

ORD record
ord-58e55d59df9f4a95a6625f46f5b6e523
Source dataset
uspto-grants-2005_02
Patent number
US06855512B2

Reaction notes

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