Synthesis of Propargylamines
by a Copper-Catalyzed Tandem Anti-Markovnikov Hydroamination
and Alkyne Addition

Lei Zhou; D. Scott Bohle; Huan-Feng Jiang; Chao-Jun Li

doi:10.1055/s-0028-1088194

LETTER

Synthesis of Propargylamines by a Copper-Catalyzed Tandem Anti-Markovnikov Hydroamination and Alkyne Addition

Lei Zhou^a,b, D. Scott Bohle^a, Huan-Feng Jiang*^b, Chao-Jun Li*^a
^a Department of Chemistry, McGill University, 801 Sherbrooke St. West, Montreal, QC, H3A 2K6, Canada
Fax: +1(514)3983797; e-Mail: cj.li@mcgill.ca;
^b College of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, P. R. of China

Abstract

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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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Referenzen

References and Notes

For recent reviews on catalytic hydroamination, see:

<A NAME="RU12208ST-1A">1a</A> Odom AL. Dalton Trans. 2005, 225

<A NAME="RU12208ST-1B">1b</A> Hultzsch KC. Adv. Synth. Catal. 2005, 347: 367

<A NAME="RU12208ST-1C">1c</A> Hong S. Marks TJ. Acc. Chem. Res. 2004, 37: 673

<A NAME="RU12208ST-1D">1d</A> Doye S. Synlett 2004, 1653

<A NAME="RU12208ST-1E">1e</A> Roesky PW. Müller TE. Angew. Chem. Int. Ed. 2003, 42: 2708

<A NAME="RU12208ST-1F">1f</A> Bytschkov I. Doye S. Eur. J. Org. Chem. 2003, 935

<A NAME="RU12208ST-1G">1g</A> Pohlki F. Doye S. Chem. Soc. Rev. 2003, 32: 104

<A NAME="RU12208ST-1H">1h</A> Alonso F. Beletskaya IP. Yus M. Chem. Rev. 2004, 104: 3079

<A NAME="RU12208ST-1I">1i</A> Severin R. Doye S. Chem. Soc. Rev. 2007, 36: 1407

<A NAME="RU12208ST-1J">1j</A> Müller TE. Hultzsch KC. Yus M. Foubelo F. Tada M. Chem. Rev. 2008, 108: 3795

<A NAME="RU12208ST-2A">2a</A> Trost BM. Angew. Chem., Int. Ed. Engl. 1995, 34: 259

<A NAME="RU12208ST-2B">2b</A> Trost BM. Science 1991, 254: 1471

<A NAME="RU12208ST-3A">3a</A> Castro CE. Stephens RD. J. Org. Chem. 1963, 28: 2163

<A NAME="RU12208ST-3B">3b</A> Stephens RD. Castro CE. J. Org. Chem. 1963, 28: 3313

<A NAME="RU12208ST-4A">4a</A> Xu L. Lewis IR. Davidsen SK. Summers JB. Tetrahedron Lett. 1998, 39: 5159

<A NAME="RU12208ST-4B">4b</A> Müller TE. Grosche M. Herdtweck E. Pleier AK. Walter E. Yan YK. Organometallics 2000, 19: 170

<A NAME="RU12208ST-4C">4c</A> Peng C. Cheng J. Wang J. Adv. Synth. Catal. 2008, 350: 2359

<A NAME="RU12208ST-4D">4d</A> Müller TE. Pleier A.-K. J. Chem. Soc., Dalton Trans. 1999, 583

<A NAME="RU12208ST-4E">4e</A> Kamijo S. Jin T. Yamamoto Y. Angew. Chem. Int. Ed. 2002, 41: 1780

<A NAME="RU12208ST-4F">4f</A> Xu L. Lewis IR. Davidsen SK. Summers JB. Tetrahedron Lett. 1998, 39: 5159

<A NAME="RU12208ST-5A">5a</A> Fukumoto Y. Asai H. Shimizu M. Chatani N. J. Am. Chem. Soc. 2007, 129: 13792

<A NAME="RU12208ST-5B">5b</A> Tzalis D. Koradin C. Knochel P. Tetrahedron Lett. 1999, 40: 6193

<A NAME="RU12208ST-5C">5c</A> Park YJ. Kwon B.-I. Ahn J.-A. Jun C.-H. J. Am. Chem. Soc. 2004, 126: 13892

<A NAME="RU12208ST-6A">6a</A> Yao X. Li C.-J. Org. Lett. 2005, 7: 4395

<A NAME="RU12208ST-6B">6b</A> Wei C. Mague JT. Li C.-J. Proc. Natl. Acad. Sci. U.S.A. 2004, 101: 5749

<A NAME="RU12208ST-6C">6c</A> Wei C. Li C.-J. J. Am. Chem. Soc. 2003, 125: 9584

<A NAME="RU12208ST-6D">6d</A> Wei C. Li Z. Li C.-J. Org. Lett. 2003, 5: 4473

<A NAME="RU12208ST-6E">6e</A> Wei C. Li C.-J. Green Chem. 2002, 4: 39

<A NAME="RU12208ST-6F">6f</A> Wei C. Li C.-J. J. Am. Chem. Soc. 2002, 124: 5638

<A NAME="RU12208ST-6G">6g</A> Li C.-J. Wei C. Chem. Commun. 2002, 268

<A NAME="RU12208ST-6H">6h</A> Zhang J. Wei C. Li C.-J. Tetrahedron Lett. 2002, 43: 5731

<A NAME="RU12208ST-6I">6i</A> Huang B. Yao X. Li C.-J. Adv. Synth. Catal. 2006, 348: 1528

<A NAME="RU12208ST-6J">6j</A> Yao X. Li C.-J. Org. Lett. 2006, 8: 1953

<A NAME="RU12208ST-6K">6k</A> Deng G. Li C.-J. Synlett 2008, 10: 1571

<A NAME="RU12208ST-6L">6l</A> Viswanathan G. Li C.-J. Tetrahedron Lett. 2002, 43: 1613

For recent examples, see:

<A NAME="RU12208ST-7A">7a</A> Asano Y. Hara K. Ito H. Sawamura M. Org. Lett. 2007, 9: 3901

<A NAME="RU12208ST-7B">7b</A> Colombo F. Benaglia M. Orlandi S. Usuelli F. Celentano G. J. Org. Chem. 2006, 71: 2064

<A NAME="RU12208ST-7C">7c</A> Arimitsu S. Hammond GB.
J. Org. Chem. 2006, 71: 8665

<A NAME="RU12208ST-7D">7d</A> Gommermann N. Koradin C. Polborn K. Knochel P. Angew. Chem. Int. Ed. 2003, 42: 5763

<A NAME="RU12208ST-7E">7e</A> Koradin C. Gommermann N. Polborn K. Knochel P. Chem. Eur. J. 2003, 9: 2797

<A NAME="RU12208ST-7F">7f</A> Lu G. Li X. Chan WL. Chan ASC. Chem. Commun. 2002, 172

<A NAME="RU12208ST-7G">7g</A> Chen ZL. Xiong WN. Jiang B. Chem. Commun. 2002, 2098

<A NAME="RU12208ST-7H">7h</A> Koradin C. Polborn K. Knochel P. Angew. Chem. Int. Ed. 2002, 41: 2535

<A NAME="RU12208ST-7I">7i</A> Carreira EM. Acc. Chem. Res. 2000, 33: 373 ; and references therein

<A NAME="RU12208ST-8A">8a</A> Zhou L. Jiang H.-F. Li C.-J. Adv. Synth. Catal. 2008, 350: 2226

For our works on silver- and gold-catalyzed hydroamination of alkynes, see:

<A NAME="RU12208ST-8B">8b</A> Luo Y. Li Z. Li C.-J. Org. Lett. 2005, 7: 2675

<A NAME="RU12208ST-8C">8c</A> Zhang Y. Donahue JP. Li C.-J. Org. Lett. 2007, 9: 627

For references on copper-catalyzed intermolecular hydroamination of olefins, see:

<A NAME="RU12208ST-9A">9a</A> Munro-Leighton C. Blue ED. Gunnoe TB. J. Am. Chem. Soc. 2006, 128: 1446

<A NAME="RU12208ST-9B">9b</A> Taylor J. Whittall N. Hii K.-K. Org. Lett. 2006, 8: 3561

For recent examples, see:

<A NAME="RU12208ST-10A">10a</A> Katagiri T. Tsurugi H. Satoh T. Miura M. Chem. Commun. 2008, 3405

<A NAME="RU12208ST-10B">10b</A> Nishimura T. Guo X.-X. Ohnishi K. Hayashi T. Adv. Synth. Catal. 2007, 349: 2669

<A NAME="RU12208ST-10C">10c</A> Tsukada N. Ninomiya S. Aoyama Y. Inoue Y. Org. Lett. 2007, 9: 2919

<A NAME="RU12208ST-10D">10d</A> Weng W. Guo C. Celenligil-Cetin R. Foxman BM. Ozerov OV. Chem. Commun. 2006, 197

<A NAME="RU12208ST-10E">10e</A> Munro-Leighton C. Delp SA. Alsop NM. Blue ED. Gunnoe TB. Chem. Commun. 2008, 111

<A NAME="RU12208ST-11A">11a</A> Zani L. Eichhorn T. Bolm C. Chem. Eur. J. 2007, 13: 2587

<A NAME="RU12208ST-11B">11b</A> Aschwanden P. Stephenson CRJ. Carreira EM. Org. Lett. 2006, 8: 2437

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.