Trimethylsilylacetylene → Methyl-(3-trimethylsilanylethynyl-benzyl)-carbamic acid tert-butyl ester

HRID 17105

Reaction equation

[Si:1]([C:5]#[CH:6])([CH3:4])([CH3:3])[CH3:2].Br[C:8]1[CH:9]=[C:10]([CH:21]=[CH:22][CH:23]=1)[CH2:11][N:12]([CH3:20])[C:13](=[O:19])[O:14][C:15]([CH3:18])([CH3:17])[CH3:16]>C(N(CC)CC)C.[Cu]I>[C:15]([O:14][C:13](=[O:19])[N:12]([CH3:20])[CH2:11][C:10]1[CH:9]=[CH:8][CH:23]=[C:22]([C:6]#[C:5][Si:1]([CH3:4])([CH3:3])[CH3:2])[CH:21]=1)([CH3:18])([CH3:17])[CH3:16]

Participants

Conditions

Temperature: 70 °C

Procedure

TMS-Acetylene (2.2 mL, 15.0 mmol) was added dropwise to commercially available tert-butyl 3-bromobenzyl(methyl)carbamate (3.0 g, 10 mmol), CuI (100 mg, 0.5 mmol) and palladium dichlorobistriphenylphosphine (210 mg, 0.3 mmol) in triethylamine (30 mL) at room temperature under a nitrogen atmosphere. The reaction mixture was heated to 70° C. for 12 hrs before cooling to room temperature and evaporating in vacuo. The residue was triturated with diethyl ether (30 mL), filtered and the filtrate evaporated in vacuo and purified by column chromatography (5% ethyl acetate in hexane) to yield A314.1 (3.2 g, 100%) as a brown oil. HPLC YMC S-5 4.6×33 mm (2 min grad): retention time 2.34 min, M+Na+=340.34

Workup

temperaturebefore cooling to room temperature
customevaporating in vacuo
customThe residue was triturated with diethyl ether (30 mL)
filtrationfiltered
customthe filtrate evaporated in vacuo
custompurified by column chromatography (5% ethyl acetate in hexane)
customto yield A314.1 (3.2 g, 100%) as a brown oil
custom4.6×33 mm (2 min grad)

Sources & evidence

ORD record: ord-153adfbc9f8a4b9bbf1463520e3cdf53
Source dataset: uspto-grants-2010_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07737279B2

Linked notes

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