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DOI: 10.1055/s-0028-1088194
Synthesis of Propargylamines by a Copper-Catalyzed Tandem Anti-Markovnikov Hydroamination and Alkyne Addition
Publikationsverlauf
Publikationsdatum:
16. März 2009 (online)

Abstract
A highly efficient tandem anti-Markovnikov hydroamination and alkyne addition reaction catalyzed by a Cu(I) or Cu(II) catalyst was developed. Various propargylamines were obtained in moderate to good yields. This tandem process provides a novel and simple approach to propargylamine derivatives from alkynes and amines.
Key words
copper - hydroamination - propargylamine - alkynes - amines
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References and Notes
Representative
Experimental Procedure
Copper(I) bromide (3.6 mg,
0.025 mmol, 5 mol%) was suspended in toluene (2 mL) in
a 10 mL Schlenk tube under nitrogen. Then, diallylamine (49 mg,
0.5 mmol) and phenylacetylene (204 mg, 2 mmol) were added. The resulting
solution was stirred at 100 ˚C for 24 h. After cooling
to r.t., the resulting mixture was filtered through a short path
of SiO2 in a pipette eluting with EtOAc. The volatiles
were removed in vacuo, and the residue was purified by column chromatography
(SiO2, hexane-EtOAc, 10:1) to give 3a (111.3 mg, 74%) as a pale yellow
oil. ¹H NMR (400 MHz, CDCl3): δ = 7.42-7.39
(m, 2 H), 7.31-7.23 (m, 8 H), 5.88-5.79 (m, 2
H), 5.23 (d, J = 17.2
Hz, 2 H), 5.13 (d, J = 10.0
Hz, 2 H), 3.97 (t, J = 7.6
Hz, 1 H), 3.41(dt, J = 14.0,
2.4 Hz, 2 H), 3.11-2.97 (m, 4 H). ¹³C
NMR (75 MHz, CDCl3): δ = 139.0, 136.6,
131.8, 129.7, 128.4, 128.3, 128.1, 126.5, 123.6, 117.5, 87.7, 86.2,
55.4, 54.3, 40.6. MS (70 eV): m/z (%) = 301 [M+],
274, 242, 215, 210(100), 191, 168, 154, 128, 115, 91. HRMS (EI): m/z calcd for C22H23N [M+]:
301.1831; found: 301.1814.
The experiments in Table
[²]
were carried out analogously.
All products were purified by column chromatography and characterized
by NMR spectroscopy and standard/high-resolution mass spectrometry.