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Synlett 2009(7): 1167-1171  
DOI: 10.1055/s-0028-1088151
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Zirconium-Catalyzed Intermolecular Hydroamination of Unactivated Olefins

Lei Yanga, Li-Wen Xu*a,b, Wei Zhoua, Yue-Hua Gaoa, Wei Suna, Chun-Gu Xia*a
a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, and Graduate School of the Chinese Academy of Sciences, Lanzhou 730000, P. R. of China
Fax: +86(931)8277088; e-Mail: lyang@lzb.ac.cn; e-Mail: cgxia@lzb.ac.cn;
b Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 310012, P. R. of China
Further Information

Publication History

Received 3 November 2008
Publication Date:
26 March 2009 (online)

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Abstract

Highly efficient hydroamination reactions of sulfon­amides, carboxamides, and carbamates with unactivated olefins catalyzed by simple and inexpensive zirconium salts under mild reaction conditions were presented for the practical preparation of various amines. These processes gave good to excellent yields of the addition products in Markovnikov addition fashion.

Key words

hydroamination - olefins - amides - carbamates - zirconium salts

    References and Notes

  • For selected recent reviews, see:
  • 1a Müller TE. Beller M. Chem. Rev.  1998,  98:  675 
    Google Scholar
  • 1b Roesky PW. Müller TE. Angew. Chem. Int. Ed.  2003,  42:  2708 
    Google Scholar
  • 1c Bystschkov I. Doye S. Eur. J. Org. Chem.  2003,  935 
    Google Scholar
  • 1d Hultzsch KC. Adv. Synth. Catal.  2005,  347:  367 
    Google Scholar
  • 1e Hazari N. Mountford P. Acc. Chem. Res.  2005,  38:  839 
    Google Scholar
  • 2a Pohlki F. Doye S. Chem. Soc. Rev.  2003,  32:  104 ; and references therein
    Google Scholar
  • 2b Hartwig JF. Pure Appl. Chem.  2004,  76:  507 
    Google Scholar
  • 2c Severin R. Doye S. Chem. Soc. Rev.  2007,  36:  1407 
    Google Scholar
  • Representative examples in the catalytic hydroamination. For lanthanide complexes, see:
  • 3a Kim YK. Livinghouse T. Horino Y. J. Am. Chem. Soc.  2003,  125:  9560 
    Google Scholar
  • 3b Kim H. Livinghouse T. Shim JH. Lee SG. Lee PH. Adv. Synth. Catal.  2006,  348:  701 ; and references cited therein
    Google Scholar
  • Alkali metals:
  • 3c Ichikawa J. Lapointe G. Iwai Y. Chem. Commun.  2007,  2698 
    Google Scholar
  • Iridium:
  • 3d Dorta R. Egli P. Zürcher F. Togni A. J. Am. Chem. Soc.  1997,  119:  10857 
    Google Scholar
  • 3e Zhao J. Goldman AS. Hartwig JF. Science  2005,  307:  1080 
    Google Scholar
  • Rhodium:
  • 3f Takemiya A. Hartwig JF. J. Am. Chem. Soc.  2006,  128:  6042 
    Google Scholar
  • 3g Beller M. Thiel OR. Trauthwein H. Hartung CG. Chem. Eur. J.  2000,  6:  2513 
    Google Scholar
  • 3h Utsunomiya M. Kuwano R. Kawatsura M. Hartwig JF. J. Am. Chem. Soc.  2003,  125:  5608 
    Google Scholar
  • Nickel:
  • 3i Pawlas J. Nakao Y. Kawatsura M. Hartwig JF. J. Am. Chem. Soc.  2002,  124:  3669 
    Google Scholar
  • 3j Fadini L. Togni A. Chem. Commun.  2003,  30 
    Google Scholar
  • Palladium:
  • 3k Minami T. Okamoto H. Ikeda S. Tanaka R. Ozawa F. Yoshifuji M. Angew. Chem. Int. Ed.  2001,  40:  4501 
    Google Scholar
  • 3l Utsunomiya M. Hartwig JF. J. Am. Chem. Soc.  2003,  125:  14286 
    Google Scholar
  • Platinum:
  • 3m Brunet JJ. Chu NC. Rodriguez-Zubiri M. Eur. J. Inorg. Chem.  2007,  4711 
    Google Scholar
  • Gold:
  • 3n Nishina N. Yamamoto Y. Angew. Chem. Int. Ed.  2006,  45:  3314 
    Google Scholar
  • 3o Han X. Widenhoefer RA. Angew. Chem. Int. Ed.  2006,  45:  1747 
    Google Scholar
  • For a review, see:
  • 3p Widenhoefer RA. Han XQ. Eur. J. Org. Chem.  2006,  4555 
    Google Scholar
  • Ruthenium:
  • 3q Utsunomiya M. Hartwig JF. J. Am. Chem. Soc.  2004,  126:  2702 
    Google Scholar
  • 3r Takaya J. Hartwig JF. J. Am. Chem. Soc.  2005,  127:  5756 
    Google Scholar
  • Main-group metals:
  • 3s Lauterwasser F. Hayes PG. Bräse S. Piers WE. Schafer LL. Organometallics  2004,  23:  2234 
    Google Scholar
  • 3t Crimmin MR. Casely IJ. Hill MS. J. Am. Chem. Soc.  2005,  127:  2042 
    Google Scholar
  • 3u Wei H. Qian GM. Xia YZ. Li K. Li YH. Li W. Eur. J. Org. Chem.  2007,  4471 
    Google Scholar
  • Brønsted acids:
  • 4a Schlummer B. Hartwig JF. Org. Lett.  2002,  4:  1471 
    Google Scholar
  • 4b Anderson LL. Arnold J. Bergman RG. J. Am. Chem. Soc.  2005,  127:  14542 
    Google Scholar
  • 4c Rosenfeld DC. Shekhar S. Takemiya A. Utsunomiya M. Hartwig JF. Org. Lett.  2006,  8:  4179 
    Google Scholar
  • 4d Marcseková I. Doye S. Synthesis  2007,  145 
    Google Scholar
  • 4e Jazzar R. Dewhurst RD. Bourg JB. Donnadieu B. Canac Y. Bertrand G. Angew. Chem. Int. Ed.  2007,  46:  2899 
    Google Scholar
  • 4f Yang L. Xu LW. Xia CG. Tetrahedron Lett.  2008,  49:  2882 
    Google Scholar
  • Recent representative progress:
  • 5a LaLonde RL. Sherry BD. Kang EJ. Toste FD. J. Am. Chem. Soc.  2007,  129:  2452 
    Google Scholar
  • 5b Wood MC. Leitch DC. Yeung CS. Kozak JA. Schafer LL. Angew. Chem. Int. Ed.  2007,  46:  354 
    Google Scholar
  • 5c Guin J. Mück-Lichtenfeld C. Grimme S. Studer A. J. Am. Chem. Soc.  2007,  129:  4498 
    Google Scholar
  • 5d Nishina N. Yamamoto Y. Synlett  2007,  1767 
    Google Scholar
  • 5e Horrillo-Martinez P. Hultzsch KC. Gil A. Branchadell V. Eur. J. Org. Chem.  2007,  3311 
    Google Scholar
  • 5f Yin Y. Ma W. Chai Z. Zhao G. J. Org. Chem.  2007,  5731 
    Google Scholar
  • 5g Lingaiah N. Babu NS. Reddy KM. Prasad PSS. Suryanarayana I. Chem. Commun.  2007,  278 
    Google Scholar
  • 5h For a review, see: Chemler SR. Fuller PH. Chem. Soc. Rev.  2007,  36:  1153 
    Google Scholar
  • 6 Ryu JS. Li GY. Marks TJ. J. Am. Chem. Soc.  2003,  125:  12584 
    CrossrefGoogle Scholar
  • 7a Qian H. Widenhoefer RA. Org. Lett.  2005,  7:  2635 
    Google Scholar
  • 7b Karshtedt D. Bell AT. Tilley TD. J. Am. Chem. Soc.  2005,  127:  12640 
    Google Scholar
  • 8a Zhang JL. Yang CG. He C. J. Am. Chem. Soc.  2006,  128:  1798 
    Google Scholar
  • 8b Liu XY. Li C. Che CM. Org. Lett.  2006,  8:  2707 
    Google Scholar
  • 8c Bender CF. Widenhoefer RA. Org. Lett.  2006,  8:  5303 
    Google Scholar
  • 8d Brouwer C. He C. Angew. Chem. Int. Ed.  2006,  45:  1744 
    Google Scholar
  • 9 Taylor JG. Whittall N. Hii KK. Org. Lett.  2006,  8:  3561 
    CrossrefPubMedGoogle Scholar
  • 10a Huang JM. Wong CM. Xu FX. Loh TP. Tetrahedron Lett.  2007,  48:  3375 
    Google Scholar
  • 10b Michaux J. Terrasson V. Marque S. Wehbe J. Prim D. Campagne JM. Eur. J. Org. Chem.  2007,  2601 
    Google Scholar
  • 10c Qin H. Matsunaga S. Yamagiwa N. Shibasaki M. Chem. Asian J.  2007,  2:  150 
    Google Scholar
  • 10d Qin H. Yamagiwa N. Matsunaga S. Shibasaki M. J. Am. Chem. Soc.  2006,  128:  1611 
    Google Scholar
  • 11a Talluri SK. Sudalai A. Org. Lett.  2005,  7:  855 
    Google Scholar
  • 11b Li Z. Zhang J. Brouwer C. Yang CG. Reich NW. He C. Org. Lett.  2006,  8:  4175 
    Google Scholar
  • 11c Rosenfeld DC. Shekhar S. Takemiya A. Utsunomiya M. Hartwig JF. Org. Lett.  2006,  8:  4179 
    Google Scholar
  • 11d Motokura K. Nakagiri N. Mori K. Mizugaki K. Ebitani T. Jitsukawa K. Kaneda K. Org. Lett.  2006,  8:  4617 
    Google Scholar
  • 12a Bytschkov I. Doye S. Eur. J. Org. Chem.  2003,  935 
    Google Scholar
  • 12b Lee AV. Schafer LL. Eur. J. Org. Chem.  2007,  2243 
    Google Scholar
  • 12c Shi Y. Ciszewski JT. Odom AL. Organometallics  2001,  20:  3967 
    Google Scholar
  • 12d Johnson JS. Bergman RG. J. Am. Chem. Soc.  2001,  123:  2923 
    Google Scholar
  • 12e Ackermann L. Organometallics  2003,  22:  4367 
    Google Scholar
  • 12f Kim H. Kim YK. Shim JH. Kim M. Han MJ. Livinghouse T. Lee PH. Adv. Synth. Catal.  2006,  348:  2609 
    Google Scholar
  • 13a Ackermann L. Kaspar LT. Gschrei CJ. Org. Lett.  2004,  6:  2515 
    Google Scholar
  • 13b Kaspar LT. Benjamin F. Ackermann L. Angew. Chem. Int. Ed.  2005,  44:  5972 
    Google Scholar
  • 13c Abbiati G. Casoni A. Canevari V. Nava D. Rossi E. Org. Lett.  2006,  8:  4839 
    Google Scholar
  • 13d Ackermann L. Kaspar LT. J. Org. Chem.  2007,  72:  6149 
    Google Scholar
  • 13e Ackermann L. Kaspar LT. Althammer A. Org. Biomol. Chem.  2007,  5:  1975 
    Google Scholar
  • Zr(OTf)4 was prepared according to reported methods:
  • 16a Kobayashi S. Iwamoto S. Nagayama S. Synlett  1997,  1099 
    Google Scholar
  • 16b Shi M. Yang YH. Xu B. Synlett  2004,  1622 
    Google Scholar
  • 17 Allylamines are fundamental building blocks in organic chemistry. For a review, see: Johannsen M. Jørgensen KA. Chem. Rev.  1998,  98:  1689 
    CrossrefGoogle Scholar
14

During the preparation of our manuscript, several related papers using other metal salts dealing with the intermolecular hydroamination of styrenes have appeared in the literature, see ref. 10a-c.

15

Typical Procedure for Intermolecular Addition Reactions of Olefins
Into a test tube were placed Zr(OTf)4 (0.05 mmol) and NH2Ts (1 mmol). After the test tube was sealed, it was purged three times with argon, then n-heptane (2 mL) and cyclohexene (2 mmol) were injected. The reaction mixture was heated at 85 ˚C and stirred vigorously for 20 h. After the reaction was completed, the mixture was directly applied to column chromatography using SiO2 (EtOAc-PE, 1:10 to 1:5) to afford a analytically pure product (93% isolated yield). All the compounds are known and NMR or GC-MS data for some representative products are given below.
N -(1-Phenylethyl)benzamide ¹H NMR (400 MHz, CDCl3): δ = 7.77 (d, J = 7.2 Hz, 2 H), 7.50-7.46 (t, 1 H), 7.42-7.35 (m, 6 H), 7.33-7.25 (m, 1 H), 6.44 (br, 1 H), 5.34 (dt, J = 7.2, 7.2 Hz, 1 H), 1.60 (d, J = 6.8 Hz, 3 H). ¹³C NMR (100 MHz, CDCl3): δ = 166.56, 143.08, 134.51, 131.42, 128.70, 128.50, 127.40, 126.89, 126.21, 49.17, 21.68. GC-MS: m/z = 225.
N -[1-(4-Bromophenyl)ethyl]-4-methylbenzenesulfon-amide
¹H NMR (400 MHz, CDCl3): δ = 7.57 (d, J = 8.4 Hz, 2 H), 7.27 (d, J = 8.4 Hz, 2 H,), 7.16 (d, J = 8.0 Hz, 2 H), 6.97 (d, J = 8.0 Hz, 2 H), 5.42 (d, J = 7.2 Hz, 1 H), 4.41 (quint, J = 6.8 Hz, 1 H), 2.39 (s, 3 H), 1.37 (d, J = 6.8 Hz, 3 H). ¹³C NMR (100 MHz, CDCl3): δ = 143.32, 140.00, 137.33, 131.43, 129.42, 127.92, 127.00, 121.16, 53.06, 23.35, 21.47. GC-MS: m/z = 354. Cyclohex-2-enyl- p -toluenesulfonamide
¹H NMR (400 MHz, CDCl3): δ = 7.75 (d, J = 7.6 Hz, 2 H), 7.27 (d, J = 8.0 Hz, 2 H), 5.71 (d, J = 10.0 Hz, 1 H), 5.31 (d, J = 10.4 Hz, 1 H), 4.84 (d, J = 8.4 Hz, 1 H), 3.77 (s, 1 H), 2.39 (s, 3 H), 1.94-1.77 (m, 2 H), 1.74-1.61 (m,1 H), 1.57-1.50 (m, 3 H). ¹³C NMR (100 MHz, CDCl3): δ = 143.14, 138.24, 131.39, 129.60, 126.95, 126.91, 48.89, 30.12, 24.38, 21.45, 19.22. GC-MS: m/z = 251.