Triethylamine → Methyl 1-(2-ethynylphenyl)cyclopropanecarboxylate

HRID 592340Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1([C:11]([O:13][CH3:14])=[O:12])[CH2:10][CH2:9]1.F[B-](F)(F)F.[C:20]([Si](C)(C)C)#[CH:21].CCN(CC)CC>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[C:20]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1([C:11]([O:13][CH3:14])=[O:12])[CH2:10][CH2:9]1)#[CH:21]

Participants

Conditions

Temperature: 65 °C

Procedure

A solution of methyl 1-(2-bromophenyl)cyclopropanecarboxylate (I4) (658 mg, 2.58 mmol), PdCl2(PPh3)2 (91 mg, 0.13 mmol) t-Bu3PH.BF4 (37 mg, 0.13 mmol), CuI (25 mg, 0.13 mmol) and ethynyltrimethylsilane (0.44 mL, 3.1 mmol) in dry DMF (5.0 mL) was degassed with nitrogen for 10 minutes before the addition of Et3N (2.0 mL). After stirring at 65° C. under nitrogen for 16 hours the resulting mixture was adsorbed onto silica gel and purified by column chromatography (Biotage Isolera, SiO2 cartridge, 0-20% EtOAc in petroleum benzine 40-60° C.) to give the title compound I5 as an orange oil (569 mg, 81%); 1H NMR (400 MHz, d6-DMSO) δ 7.67-7.12 (m, 4H), 3.57-3.47 (m, 3H), 1.64-1.49 (m, 2H), 1.26-1.16 (m, 2H), 0.22-0.13 (m, 9H). LCMS-A: rt 6.977 min; m/z 273 [M+H]+.

Workup

custompurified by column chromatography (Biotage Isolera, SiO2 cartridge, 0-20% EtOAc in petroleum benzine 40-60° C.)

Sources & evidence

ORD record: ord-4da086c38ce546278db57fdc05d8190d
Source dataset: uspto-grants-2016_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09238644B2

Reaction notes

Loading…