Silane, (1,1-dimethylethyl)[(1,1-dimethyl-2-propynyl)oxy]dimethyl- → 4-[3-(Tert-butyl-dimethyl-silanyloxy)-3-methyl-but-1-ynyl]-6-(2,6-diethyl-phenyl)-2-methyl-nicotinic acid ethyl ester

HRID 251625Notes

Reaction equation

HRID 251625 reaction equation
[CH2:1]([O:3][C:4](=[O:23])[C:5]1[C:10](Br)=[CH:9][C:8]([C:12]2[C:17]([CH2:18][CH3:19])=[CH:16][CH:15]=[CH:14][C:13]=2[CH2:20][CH3:21])=[N:7][C:6]=1[CH3:22])[CH3:2].[C:24]([Si:28]([O:31][C:32]([CH3:36])([CH3:35])[C:33]#[CH:34])([CH3:30])[CH3:29])([CH3:27])([CH3:26])[CH3:25]>C(NC(C)C)(C)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)I>[CH2:1]([O:3][C:4](=[O:23])[C:5]1[C:10]([C:34]#[C:33][C:32]([O:31][Si:28]([C:24]([CH3:27])([CH3:26])[CH3:25])([CH3:30])[CH3:29])([CH3:36])[CH3:35])=[CH:9][C:8]([C:12]2[C:17]([CH2:18][CH3:19])=[CH:16][CH:15]=[CH:14][C:13]=2[CH2:20][CH3:21])=[N:7][C:6]=1[CH3:22])[CH3:2]

Participants

6

Reactant 2

HCID 11084826Silane, (1,1-dimethylethyl)[(1,1-dimethyl-2-propynyl)oxy]dimethyl-HCID 669935654-Bromo-6-(2,6-diethyl-phenyl)-2-methyl-nicotinic ethyl ester

Product 1

HCID 669945234-[3-(Tert-butyl-dimethyl-silanyloxy)-3-methyl-but-1-ynyl]-6-(2,6-diethyl-phenyl)-2-methyl-nicotinic acid ethyl ester

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 7912DiisopropylamineSolvent

Conditions

Temperature
105 °C

Procedure

A mixture of 4-bromo-6-(2,6-diethyl-phenyl)-2-methyl-nicotinic ethyl ester (274 mg, 0.73 mmol), tert-butyl-(1,1-dimethyl-prop-2-ynyloxy)-dimethyl-silane (724 mg, 0.37 mmol), Pd(PPh3)4 (84 mg, 0.082 mmol), and copper iodide (7 mg, 0.037 mmol) in diisopropylamine (8 mL) is heated at 105° C. in a scaled tube. The filtrate is concentrated in vacuo. The residue is purified by flash chromatography to give 4-[3-(tert-butyl-dimethyl-silanyloxy)-3-methyl-but-1-ynyl]-6-(2,6-diethyl-phenyl)-2-methyl-nicotinic acid ethyl ester as a pale yellow oil. 1H NMR (CDCl3) 7.38-7.31 (m, 2H), 7.17-7.12 (m, 2H), 4.43 (q, 2H), 2.62 (s, 3H), 2.38-2.25 (m, 4H), 1.56 (s, 6H), 1.44 (t, 3H), 1.06 (t, 6H), 0.83 (s, 9H), 0.15 (s, 6H).

Workup

  1. concentrationThe filtrate is concentrated in vacuo
  2. customThe residue is purified by flash chromatography

Sources & evidence

ORD record
ord-c298657f0ed542fca0a6af08e1e8a323
Source dataset
uspto-grants-2011_01
Patent number
US07863454B2

Reaction notes

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