An Efficient Ring-Opening Reaction of Aziridines with Alkynes Catalyzed by CuOTf

Chang-Hua Ding; Li-Xin Dai; Xue-Long Hou

doi:10.1055/s-2004-829551

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Synlett 2004(10): 1691-1694
DOI: 10.1055/s-2004-829551

LETTER

An Efficient Ring-Opening Reaction of Aziridines with Alkynes Catalyzed by CuOTf

Chang-Hua Ding^b, Li-Xin Dai^a, Xue-Long Hou*^a,b
^a State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, China
^b Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, China
e-Mail: xlhou@mail.sioc.ac.cn;

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Publication History

Received 9 April 2004
Publication Date:
15 July 2004 (online)

Abstract
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Abstract

The alkynylation of activated aziridines in the presence of a catalytic amount of CuOTf provided the corresponding ring-opened products in high yields.

Key words

aziridines - alkynylation - Lewis acids - copper(I) triflate - ring-opening reaction

References

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8

General Experimental Procedure: Alkyne (0.5 mmol) was added to a mixture of n-BuLi in n-hexane (0.5 mmol) and Et₂O (4.0 mL), which was precooled to -78 °C and the mixture was stirred for 30 min at the same temperature. Then CuOTf (10 mol%) and aziridine (0.25 mmol) were added. The resulting mixture was stirred at r.t. until complete consumption of substrate (monitored by TLC). The reaction mixture was quenched with 5 mL of sat. NH₄Cl aq solution. The aqueous layer was separated and extracted with CH₂Cl₂ (3 ¥ 10 mL). The combined organic layer was dried over anhyd Na₂SO₄. The solvent was removed in vacuum and the crude product was purified by flash column chromatography on silica gel to provide corresponding homopropargyl amine. All products were fully characterized by ¹H NMR, mass spectrometry, infrared spectrometry and elemental analysis. The ¹H NMR spectra of the products are as follows (300 MHz, CDCl₃, 25 °C, TMS):
N -(2-Phenyl-1-ynyl-cyclohexyl)-4-methyl-benzene-sulfonamide (2a): ¹H NMR: δ = 1.24-1.27 (m, 4 H), 1.46-1.69 (m, 2 H), 1.99-2.05 (m, 1 H), 2.24-2.28 (m, 1 H), 2.31 (s, 3 H), 2.41-2.49 (m, 1 H), 3.02-3.12 (m, 1 H), 4.81 (d, J = 5.4 Hz, 1 H), 7.11 (d, J = 8.1 Hz, 2 H), 7.12-7.29 (m, 5 H), 7.75 (d, J = 8.4 Hz, 2 H).
N -(2-phenyl-1-ynyl-cyclopentyl)-4-methyl-benzene-sulfonamide (2b): ¹H NMR: δ = 1.45-1.53 (m, 1 H), 1.68-1.75 (m, 3 H), 2.04-2.15 (m, 2 H), 2.32 (s, 3 H), 2.69-2.74 (m, 1 H), 3.52-3.56 (m, 1 H), 4.80 (d, J = 6.0 Hz, 1 H), 7.20 (d, J = 8.1 Hz, 2 H), 7.23-7.29 (m, 5 H), 7.78-7.82 (m, 2 H).
N -(2-phenyl-1-ynyl-cyclohexyl)-benzenesulfonamide (2c): ¹H NMR: δ = 1.21-1.69 (m, 6 H), 1.99-2.05 (m, 1 H), 2.23-2.27 (m, 1 H), 2.42-2.50 (m, 1 H), 3.07-3.13 (m, 1 H), 4.88 (d, J = 5.4 Hz, 1 H), 7.24-7.47 (m, 8 H), 7.87-7.89 (m, 2 H).
N -(2-trimethylsilanyl-1-ynyl-cyclohexyl)-4-methyl-benzenesulfonamide (2aa): ¹H NMR: δ = 0.13 (s, 9 H), 1.48-1.64 (m, 6 H), 1.89-1.94 (m, 1 H), 2.21-2.33 (m, 2 H), 2.43 (s, 3 H), 2.89-2.94 (m, 1 H), 4.80 (d, J = 3.6 Hz, 1 H), 7.31 (d, J = 8.4 Hz, 2 H), 7.78 (d, J = 8.4 Hz, 2 H).
1-Phenyl-4- N -( p -toluenesulfonyl)aminooctyne-1 (2d): ¹H NMR: δ = 0.82 (t, J = 6.6 Hz, 3 H), 1.19-1.25 (m, 4 H), 1.56-1.62 (m, 2 H), 2.41 (s, 3 H), 2.48 (d, J = 5.1 Hz, 2 H), 3.36-3.46 (m, 1 H), 4.71 (d, J = 9.3 Hz, 1 H), 7.26-7.37 (m, 7 H), 7.78 (d, J = 8.1 Hz, 2 H).
1-Phenyl-5,5-dimethyl-4- N -( p -toluenesulfonyl)amino-hexyne-1 (2e): ¹H NMR: d = 0.98 (s, 9H), 2.28-2.36 (m, 1H), 2.39 (s, 3H), 2.49-2.56 (m, 1H), 3.16-3.23 (m, 1H), 4.89 (d, J = 10.5 Hz, 1H), 7.24-7.35 (m, 7H), 7.79 (d, J = 8.1 Hz, 2H).
1-Phenyl-4- N -( p -toluenesulfonyl)aminodecyne-1 (2f):
¹H NMR: δ = 0.85 (t, J = 6.9 Hz, 3 H), 1.17-1.29 (m, 8 H), 1.52-1.62 (m, 2 H), 2.41 (s, 3 H), 2.50 (d, J = 4.8 Hz, 2 H), 3.37-3.45 (m, 1 H), 4.67 (d, J = 9.0 Hz, 1 H), 7.26-7.38 (m, 7 H), 7.78 (d, J = 8.1 Hz, 2 H).
1-Phenyl-4- N -( p -toluenesulfonyl)aminoicosyne-1 (2g): ¹H NMR: δ = 0.88 (t, J = 6.6 Hz, 3 H), 1.17-1.30 (m, 28 H), 1.57-1.64 (m, 2 H), 2.41 (s, 3 H), 2.49 (d, J = 4.8 Hz, 2 H), 3.36-3.44 (m, 1 H), 4.65 (d, J = 9.3 Hz, 1 H), 7.26-7.38 (m, 7 H), 7.77-7.79 (m, 2 H).
1-Trimethylsilanyl-4- N -( p -toluenesulfonyl)amino-decyne-1 (2fa): ¹H NMR: δ = 0.15 (s, 9 H), 0.85 (t, J = 6.9 Hz, 3 H), 1.15-1.26 (m, 8 H), 1.88-2.04 (m, 2 H), 2.27-2.31 (m, 2 H), 2.43 (s, 3 H), 3.28-3.33 (m, 1 H), 4.61 (d, J = 9.0 Hz, 1 H), 7.30 (d, J = 7.5 Hz, 2 H), 7.76 (d, J = 8.4 Hz, 2 H).
8- N -( p -toluenesulfonyl)aminotetradecyne-5 (2fb): ¹H NMR: δ = 0.85 (t, J = 6.6 Hz, 3 H), 0.91 (t, J = 7.2 Hz, 3 H), 1.16-1.25 (m, 8 H), 1.38-1.47 (m, 6 H), 2.12-2.16 (m, 2 H), 2.17-2.21 (m, 2 H), 2.43 (s, 3 H), 3.24-3.31 (m, 1 H), 4.63 (d, J = 9.6 Hz, 1 H), 7.29 (d, J = 7.5 Hz, 2 H), 7.75-7.78 (m, 2 H).
1,4-Diphenyl-4- N -( p -toluenesulfonyl)aminobutyne-1 (2h) and 1,3-Diphenyl-4- N -( p -toluenesulfonyl)amino-butyne-1 (3h): (2h/3h = 3:1) ¹H NMR: 2h: δ = 2.35 (s, 3 H), 2.85 (m, 2 H), 4.56 (dd, J = 6.3, 12.8 Hz, 1 H), 5.20 (d, J = 6.6 Hz, 1 H), 7.12-7.41 (m, 12 H), 7.63 (d, J = 8.4 Hz, 2 H); 3h: δ = 2.41 (s, 3 H), 3.21-3.41 (m, 2 H), 3.99 (dd, J = 6.3, 8.1 Hz, 1 H), 4.72-4.76 (m, 1 H), 7.12-7.41 (m, 12 H), 7.73 (d, J = 8.4 Hz, 2 H).