Triethylamine → 3-Bromo-5-(prop-1-yn-1-yl)pyridine

HRID 1907417Notes

Reaction equation

HRID 1907417 reaction equation
C[Si](C)(C)[C:3]#[C:4][CH3:5].Br[C:9]1[CH:10]=[N:11][CH:12]=[C:13]([Br:15])[CH:14]=1.CCCC[N+](CCCC)(CCCC)CCCC.[F-].C(N(CC)CC)C>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I.O.CCOC(C)=O>[Br:15][C:13]1[CH:12]=[N:11][CH:10]=[C:9]([C:3]#[C:4][CH3:5])[CH:14]=1

Participants

9

Reactant 4

HCID 8471TriethylamineHCID 693693,5-DibromopyridineHCID 803631-(Trimethylsilyl)prop-1-yneHCID 2724141Tetrabutylammonium Fluoride

Product 1

HCID 574665963-Bromo-5-(prop-1-yn-1-yl)pyridineYield 42.7%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of trimethyl(prop-1-yn-1-yl)silane (1.7 g, 11.48 mmol), 3,5-dibromopyridine (2.72 g, 11.48 mmol), Pd(PPh3)4 (0.66 g, 0.57 mmol), TBAF (1.0 M solution in THF, 11.48 mL, 11.48 mmol), copper(I) iodide (0.66 g, 3.44 mmol), and triethylamine (5.28 mL, 37.9 mmol) was stirred at rt for 12 h. The reaction mixture was worked up with EtOAc and water, and the crude product was purified by silica gel chromatography eluting with 0-3% EtOAc/Hexanes to give the title compound as a white solid (0.96 g, 42% yield). 1H NMR (400 MHz, CHLOROFORM-d) δ 8.55 (dd, J=12.3, 2.0 Hz, 2H), 7.83 (t, J=1.9 Hz, 1H), 2.10 (s, 3H).

Workup

  1. customthe crude product was purified by silica gel chromatography
  2. washeluting with 0-3% EtOAc/Hexanes

Sources & evidence

ORD record
ord-18667f7e12984d6ca36605fdac789c2d
Source dataset
uspto-grants-2013_12
Patent number
US08598161B2

Reaction notes

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