Triethylamine → Methyl 2-(methoxymethylene)-4-(trimethylsilyl)but-3-ynoate

HRID 1525337Notes

Reaction equation

I[C:2](=[CH:7][O:8][CH3:9])[C:3]([O:5][CH3:6])=[O:4].[C:10]([Si:12]([CH3:15])([CH3:14])[CH3:13])#[CH:11].C(N(CC)CC)C>CN(C=O)C.[Cu]I.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:9][O:8][CH:7]=[C:2]([C:11]#[C:10][Si:12]([CH3:15])([CH3:14])[CH3:13])[C:3]([O:5][CH3:6])=[O:4]

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of compound 37-g (30 g, 124 mmol), ethynyltrimethylsilane (24.3 g, 248 mmol), triethylamine (37.6 g, 372 mmol), copper(I) iodide (2.35 g, 6.2 mmol), Pd(dppf)Cl2 (2.50 g) in DMF (300 mL) was stirred overnight at 80° C. The reaction mixture was cooled to room temperature, poured into ice-water, and extracted with ethyl acetate. The organic layer was washed with water, brine, and dried over sodium sulfate and concentrated. The residue was purified by flash chromatography (PE:EA=1:5) to afford compound 37-h (15 g, 57%) as a yellow solid. 1H NMR (300 MHz, CDCl3) δ 7.671 (s, 1H), 3.977 (s, 3H), 3.763 (s, 3H), 0.234 (s, 9H); LC-MS (ESI): 213 [M+H]+.

Workup

temperatureThe reaction mixture was cooled to room temperature
extractionextracted with ethyl acetate
washThe organic layer was washed with water, brine
dry with materialdried over sodium sulfate
concentrationconcentrated
customThe residue was purified by flash chromatography (PE:EA=1:5)

Sources & evidence

ORD record: ord-0c0335406a8d4591b41d460b8d9b2552
Source dataset: uspto-grants-2015_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09079930B2

Reaction notes

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