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

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;

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

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References

1a McCoull W. Davis FA. Synthesis 2000, 1347

1b Tanner D. Angew. Chem., Int. Ed. Engl. 1994, 33: 599

1c Kump JEG. In Comprehensive Organic Synthesis Vol. 7: Trost BM. Fleming I. Pergamon; Oxford: 1991. p.467

For examples of the reaction of aziridine with alcohols or phenols see:

2a Jacques B. Josette CR. Roger V. Synthesis 1992, 288

2b Bellos K. Stamm H. J. Org. Chem. 1995, 60: 5661

2c Wipf P. Uto Y. Tetrahedron Lett. 1999, 40: 5165

2d Stamm H. Schneider L. Chem. Ber. 1974, 107: 2870

For examples of the reaction of aziridine with thiols see:

3a Antolini L. Bucciarelli M. Caselli E. Davoli P. Forni A. Moretti I. Prati F. Torre G. J. Org. Chem. 1997, 62: 8784

3b Maligres PE. See MM. Askin D. Reider PJ. Tetrahedron Lett. 1997, 38: 5253

3c Bae JH. Shin SH. Park CS. Lee WK. Tetrahedron 1999, 55: 10041

3d Katagiri T. Takahashi M. Fujiwara Y. Ihara H. Uneyama K. J. Org. Chem. 1999, 64: 7323

3e Wu J. Hou XL. Dai LX. J. Chem. Soc., Perkin Trans. 1 2001, 1314

For examples of the reaction of aziridine with amines see:

4a Nakajima K. Tanaka T. Morita K. Okawa K. Bull. Chem. Soc. Jpn. 1980, 53: 283

4b Meguro M. Yamamoto Y. Heterocycles 1996, 43: 2473

4c Lucet D. Gallo TL. Mioskowski C. Angew. Chem. Int. Ed. 1998, 37: 2580

4d Sekar G. Singh VK. J. Org. Chem. 1999, 64: 2537

5a Oppolzer W. Flaskamp E. Helv. Chim. Acta 1977, 60: 204

5b Osborn HM. Sweeney JB. Howson B. Synlett 1993, 675

5c Tanner D. He HM. Somfai P. Tetrahedron 1992, 48: 6069

5d Baldwin JE. Adlington RM. Robinson NG. J. Chem. Soc., Chem. Commun. 1987, 153

5e Lygo B. Synlett 1993, 764

5f Dubois L. Mehta A. Tourette E. J. Org. Chem. 1994, 59: 434

5g Bouayed Z. Chanet-Ray J. Ducher S. Vessiere R. J. Heterocycl. Chem. 1991, 28: 1757

5h Müller P. Nury P. Org. Lett. 1999, 1: 439

6a Gronquist MR. Meinwald J. J. Org. Chem. 2001, 66: 1075

6b Rainier JD. Imbriglio JE. J. Org. Chem. 2000, 65: 7272

6c Daub GW. Heering DA. Overman LA. Tetrahedron 1988, 44: 3919

6d Compain P. Goré J. Vatèle JM. Tetrahedron 1996, 52: 10405

6e Church NJ. Young DW. Tetrahedron Lett. 1995, 36: 151

6f Ooi T. Kagoshima N. Ichikama H. Maruoka K. J. Am. Chem. Soc. 1999, 121: 3328

6g Fuji K. Kawabata T. Kiryu Y. Sugiura Y. Heterocycle 1996, 42: 701

7a Li AH. Dai LX. Hou XL. Chem. Commun. 1996, 491

7b Li AH. Dai LX. Hou XL. Chen MB. J. Org. Chem. 1996, 61: 4641

7c Wang DK. Dai LX. Hou XL. Chem. Commun. 1997, 1231

7d Li AH. Zhou YG. Dai LX. Hou XL. Xia LJ. Lin L. Angew. Chem., Int. Ed. Engl. 1997, 36: 1317

7e Hou XL. Yang XF. Dai LX. Chen XF. Chem. Commun. 1998, 747

7f Wu J. Hou XL. Dai LX. J. Org. Chem. 2000, 65: 1344

7g Hou XL. Fan RH. Dai LX. J. Org. Chem. 2002, 67: 5295

7h Fan RH. Hou XL. J. Org. Chem. 2003, 68: 726

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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).