Trimethyl((tributylstannyl)ethynyl)silane → HCID 90409361, compound

HRID 516579Notes

Reaction equation

HRID 516579 reaction equation
[NH2:1][C:2]1[C:7]([CH3:8])=[C:6]([C:9]2[CH:14]=[CH:13][C:12](I)=[CH:11][CH:10]=2)[N:5]=[C:4]([C:16]([O:18][CH3:19])=[O:17])[C:3]=1[Cl:20].[CH3:21][Si:22]([CH3:39])([CH3:38])[C:23]#[C:24][Sn](CCCC)(CCCC)CCCC>CN(C=O)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>[NH2:1][C:2]1[C:7]([CH3:8])=[C:6]([C:9]2[CH:14]=[CH:13][C:12]([C:24]#[C:23][Si:22]([CH3:39])([CH3:38])[CH3:21])=[CH:11][CH:10]=2)[N:5]=[C:4]([C:16]([O:18][CH3:19])=[O:17])[C:3]=1[Cl:20]

Participants

5

Reactant 2

HCID 639663Trimethyl((tributylstannyl)ethynyl)silaneHCID 90409363HCID 90409363, compound

Product 1

HCID 90409361HCID 90409361, compoundYield 21.1%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of methyl 4-amino-3-chloro-6-(4-iodophenyl)-5-methylpicolinate (264 mg, 0.66 mmol), trimethyl((tributylstannyl)ethynyl)silane (280 mg, 0.72 mmol), tetrakis(triphenylphosphine)palladium(0) (75 mg, 0.065 mmol) in anhydrous DMF (1.3 mL) was heated at 90° C. for 16 h. The reaction was cooled, diluted water, and extracted with ethyl acetate (2×). The organic layers were dried over anhydrous magnesium sulfate, filtered, and adsorbed onto silica gel. Purification by flash chromatography (0-100% ethyl acetate/hexanes) afforded the title compound as a brown solid (52 mg, 21%): mp 158-164° C.; 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J=8.5 Hz, 2H), 7.40 (d, J=8.5 Hz, 2H), 4.83 (s, 2H), 3.96 (s, 3H), 2.14 (s, 3H), 0.26 (s, 9H); IR (neat film) 3325, 3227, 2955, 2157, 1729, 1629, 1246 cm−1; ESIMS m/z 372 ([M]+).

Workup

  1. temperatureThe reaction was cooled
  2. extractiondiluted water, and extracted with ethyl acetate (2×)
  3. dry with materialThe organic layers were dried over anhydrous magnesium sulfate
  4. filtrationfiltered
  5. customPurification by flash chromatography (0-100% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-610848aa35004187beaabba6ff3c830e
Source dataset
uspto-grants-2015_08
Patent number
US09113629B2

Reaction notes

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