Download PDF
Synlett 2010(13): 2002-2008  
DOI: 10.1055/s-0030-1258128
CLUSTER
© Georg Thieme Verlag Stuttgart ˙ New York

Magnetically Recoverable Iron Nanoparticle Catalyzed Cross-Dehydrogena­tive Coupling (CDC) between Two Csp³-H Bonds Using Molecular Oxygen

Tieqiang Zenga,b, Gonghua Song*b, Audrey Mooresa, 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 Shanghai Key Laboratory of Chemical Biology, Institute of Pesticides and Pharmaceuticals, East China University of Science and Technology, Shanghai 200237, P. R. of China
Fax: +86(21)64252603; e-Mail: ghsong@ecust.edu.cn;
Further Information

Publication History

Received 19 April 2010
Publication Date:
09 July 2010 (online)

   Permissions and Reprints All articles of this category
Preview

Abstract

The oxidative C-C bond formations between Csp³-H bond adjacent to nitrogen and Csp³-H bond of nitroalkanes are catalyzed efficiently by magnetically recoverable iron nanoparticles using oxygen. The catalyst can be magnetically removed and recycled easily for nine times without decreasing activity.

Key words

iron nanoparticles - oxygen - cross-coupling - C-C bond formation

    References and Notes

  • 1a Trost BM. Acc. Chem. Res.  2002,  35:  695 
    Search in Google Scholar
  • 1b Li C.-J. Trost BM. Proc. Natl. Acad. Sci. U.S.A.  2008,  105:  13197 
    Search in Google Scholar
  • 1c Anastas PT. Kirchhoff MM. Acc. Chem. Res.  2002,  35:  686 
    Search in Google Scholar
  • 2a Trost BM. Science  1991,  254:  1471 
    Search in Google Scholar
  • 2b Anastas PT. Warner JC. Green Chemistry: Theory and Practice   Oxford University Press; Oxford: 1998. 
  • 2c Jenck JF. Agterberg F. Droescher MJ. Green Chem.  2004,  6:  544 
    Search in Google Scholar
  • 3 Corey EJ. Cheng XM. The Logic of Chemical Synthesis   John Wiley and Sons; New York: 1989. 
  • 4a Godula K. Sames D. Science  2006,  312:  67 
    Search in Google Scholar
  • 4b Bergman RG. Nature (London)  2007,  446:  391 
    Search in Google Scholar
  • 4c Jia C. Kitamura T. Fujiwara Y. Acc. Chem. Res.  2001,  34:  633 
    Search in Google Scholar
  • 4d Ritleng V. Sirlin C. Pfeffer M. Chem. Rev.  2002,  102:  1731 
    Search in Google Scholar
  • 4e Yu J.-Q. Giri R. Chen X. Org. Biomol. Chem.  2006,  4:  4041 
    Search in Google Scholar
  • 4f Alberico D. Scott ME. Lautens M. Chem. Rev.  2007,  107:  174 
    Search in Google Scholar
  • 4g Herrerias CI. Yao X. Li Z. Li C.-J. Chem. Rev.  2007,  107:  2546 
    Search in Google Scholar
  • 4h Seregin IV. Gevorgyan V. Chem. Soc. Rev.  2007,  36:  1173 
    Search in Google Scholar
  • 4i Giri R. Shi B.-F. Engle KM. Maugel N. Yu J.-Q. Chem. Soc. Rev.  2009,  38:  3242 
    Search in Google Scholar
  • 4j Ackermann L. Pure. Appl. Chem.  2010,  82:  1403 
    Search in Google Scholar
  • Selected examples of CDC reaction, see:
  • 5a Li C.-J. Acc. Chem. Res.  2009,  42:  335 
    Search in Google Scholar
  • 5b Zhao L. Baslé O. Li C.-J. Proc. Natl. Acad. Sci. U.S.A.  2009,  106:  4106 
    Search in Google Scholar
  • 5c Deng G. Li C.-J. Org. Lett.  2009,  11:  1171 
    Search in Google Scholar
  • 5d Zhao L. Li C.-J. Angew. Chem. Int. Ed.  2008,  47:  7075 
    Search in Google Scholar
  • 5e Deng G. Zhao L. Li C.-J. Angew. Chem. Int. Ed.  2008,  47:  6278 
    Search in Google Scholar
  • 5f Li Z. Cao L. Li C.-J. Angew. Chem. Int. Ed.  2007,  46:  6505 
    Search in Google Scholar
  • 5g Zhang Y. Li C.-J. Eur. J. Org. Chem.  2007,  4654 
  • 5h Li Z. Bohle DS. Li C.-J. Proc. Natl. Acad. Sci. U.S.A.  2006,  103:  8928 
    Search in Google Scholar
  • 5i Li Z. Li C.-J. J. Am. Chem. Soc.  2006,  128:  56 
    Search in Google Scholar
  • 5j Li Z. Li C.-J. Eur. J. Org. Chem.  2005,  3173 
  • 5k Li Z. Li C.-J. J. Am. Chem. Soc.  2005,  127:  6968 
    Search in Google Scholar
  • 5l Li Z. Li C.-J. J. Am. Chem. Soc.  2005,  127:  3672 
    Search in Google Scholar
  • 5m Li Z. Li C.-J. Org. Lett.  2004,  6:  4997 
    Search in Google Scholar
  • 5n Li Z. Li C.-J. J. Am. Chem. Soc.  2004,  126:  11810 
    Search in Google Scholar
  • 5o Baslé O. Li C.-J. Green Chem.  2007,  9:  1047 
    Search in Google Scholar
  • 5p Baslé O. Li C.-J. Chem. Commun.  2009,  4124 
  • For examples, see:
  • 6a Sud A. Sureshkumar D. Klussmann M. Chem. Commun.  2009,  3169 
  • 6b Shen Y. Li M. Wang S. Zhan T. Tan Z. Guo C.-C. Chem. Commun.  2009,  953 
  • 6c Jin J. Li Y. Wang Z.-J. Qian W.-X. Bao W.-L. Eur. J. Org. Chem.  2010,  1235 
  • 6d Maheswari CU. Kumar GS. Venkateshwar M. Kumar RA. Kantam ML. Reddy KR. Adv. Synth. Catal.  2010,  352:  341 
    Search in Google Scholar
  • 6e Cai G. Fu Y. Li Y. Wan X. Shi Z. J. Am. Chem. Soc.  2007,  129:  7666 
    Search in Google Scholar
  • 6f Stuart DR. Fagnou K. Science  2007,  316:  1172 
    Search in Google Scholar
  • 6g Dwight TA. Rue NR. Charyk D. Josselyn R. DeBoef B. Org. Lett.  2007,  9:  3137 
    Search in Google Scholar
  • 6h Hull KL. Sanford MS. J. Am. Chem. Soc.  2007,  129:  11904 
    Search in Google Scholar
  • 6i Xia J.-B. You S.-L. Organometallics  2007,  26:  4869 
    Search in Google Scholar
  • 6j Yu A. Gu Z. Chen D. He W. Tan P. Xiang J. Catal. Commun.  2009,  11:  162 
    Search in Google Scholar
  • 6k Li Y.-Z. Li B.-J. Lu X.-Y. Lin S. Shi Z.-J. Angew. Chem. Int. Ed.  2009,  48:  3817 
    Search in Google Scholar
  • 6l Anaya de Parrodi C. Walsh PJ. Angew. Chem. Int. Ed.  2009,  48:  4679 
    Search in Google Scholar
  • 6m Li B.-J. Tian S.-L. Fang Z. Shi Z.-J. Angew. Chem. Int. Ed.  2008,  47:  1115 
    Search in Google Scholar
  • 6n Catino AJ. Nichols JM. Nettles BJ. Doyle MP. J. Am. Chem. Soc.  2006,  128:  5648 
    Search in Google Scholar
  • 6o Murahashi S.-I. Nakae T. Terai H. Komiya N. J. Am. Chem. Soc.  2008,  130:  11005 
    Search in Google Scholar
  • 6p Tsang AS.-K. Todd MH. Tetrahedron Lett.  2009,  50:  1199 
    Search in Google Scholar
  • 6q Condie AG. González-Gómez JC. Stephenson CRJ. J. Am. Chem. Soc.  2010,  132:  1464 
    Search in Google Scholar
  • For examples, see:
  • 7a Latham AH. Williams ME. Acc. Chem. Res.  2008,  41:  411 
    Search in Google Scholar
  • 7b Laurent S. Forge D. Port M. Roch A. Robic C. Vander Elst L. Muller RN. Chem. Rev.  2008,  108:  2064 
    Search in Google Scholar
  • 7c Sun S. Zeng H. J. Am. Chem. Soc.  2002,  124:  8204 
    Search in Google Scholar
  • For selected reviews on Fe catalysis, see:
  • 7d Bolm C. Legros J. Le Paih J. Zani L. Chem. Rev.  2004,  104:  6217 
    Search in Google Scholar
  • 7e Sarhan AAO. Bolm C. Chem. Soc. Rev.  2009,  38:  2730 
    Search in Google Scholar
  • 7f Morris RH. Chem. Soc. Rev.  2009,  38:  2282 
    Search in Google Scholar
  • 7g Cheng ZY. Li YZ. Chem. Rev.  2007,  107:  748 
    Search in Google Scholar
  • 7h Sherry BD. Fürstner A. Acc. Chem. Res.  2008,  41:  1500 
    Search in Google Scholar
  • 8 Guin D. Baruwati B. Manorama SV. Org. Lett.  2007,  9:  1419 
    CrossrefSearch in Google Scholar
  • For examples, see:
  • 9a Polshettiwar V. Baruwati B. Varma RS. Chem. Commun.  2009,  1837 
  • 9b Luo S. Zheng X. Xu H. Mi X. Zhang L. Cheng J.-P. Adv. Synth. Catal.  2007,  349:  2431 
    Search in Google Scholar
  • 9c Polshettiwar V. Baruwati B. Varma RS. Green Chem.  2009,  11:  127 
    Search in Google Scholar
  • 9d Kotani M. Koike T. Yamaguchi K. Mizuno N. Green Chem.  2006,  8:  735 
    Search in Google Scholar
  • 9e Zhang D.-H. Li G.-D. Lia J.-X. Chen J.-S. Chem. Commun.  2008,  3414 
  • 9f Kawamura M. Sato K. Chem. Commun.  2006,  4718 
  • 9g Kawamura M. Sato K. Chem. Commun.  2007,  3404 
  • 9h Hu A. Yee GT. Lin W. J. Am. Chem. Soc.  2005,  127:  12486 
    Search in Google Scholar
  • 9i Chouhan G. Wang D. Alper H. Chem. Commun.  2007,  4809 
  • 9j Abu-Reziq R. Wang D. Post M. Alper H. Adv. Synth. Catal.  2007,  349:  2145 
    Search in Google Scholar
  • 9k Polshettiwar V. Varma RS. Chem. Eur. J.  2009,  15:  1582 
    Search in Google Scholar
  • 9l Ge J. Zhang Q. Zhang T. Yin Y. Angew. Chem. Int. Ed.  2008,  47:  8924 
    Search in Google Scholar
  • 10 Zeng T. Chen W.-W. Cirtiu CM. Moores A. Song G. Li C.-J. Green Chem.  2010,  12:  570 
    CrossrefSearch in Google Scholar
  • 11a Wu X.-J. Jiang R. Wu B. Su X.-M. Xu X.-P. Ji S.-J. Adv. Synth. Catal.  2009,  351:  3150 
    Search in Google Scholar
  • 11b Sreedhar B. Kumar AS. Reddy PS. Tetrahedron Lett.  2010,  51:  1891 
    Search in Google Scholar
  • 12a Buchwald SL. Bolm C. Angew. Chem. Int. Ed.  2009,  48:  5586 
    Search in Google Scholar
  • 12b Larsson P.-F. Correa A. Carril M. Norrby P.-O. Bolm C. Angew. Chem. Int. Ed.  2009,  48:  5691 
    Search in Google Scholar
  • 14 Evans DA. Seidel D. Rueping M. Lam HW. Shaw JT. Downey CW. J. Am. Chem. Soc.  2003,  125:  12692 
    CrossrefPubMedSearch in Google Scholar
  • 16 Kwong FY. Klapars A. Buchwald SL. Org. Lett.  2002,  4:  581 
    CrossrefPubMedSearch in Google Scholar
13

The leaching of Fe residue in the resulting crude material was detected by Thermo Jarrell Ash ICP-AES. No obvious Fe leaching was detected (below detecting limit).

15

Experimental Procedure
Fe3O4 [<50 nm particle size (TEM)], Fe2O3 (<50 nm particle size) and other reagents were purchased from Sigma-Aldrich and used without further purification. 2-Aryl-1,2,3,4-tetrahydroisoquinolines were prepared by the literature method.¹6 To a reaction tube charged with a magnetic stir bar and Fe3O4 nanoparticles (0.02 mmol, 10 mol%), 1,2,3,4-tetrahydroisoquinoline derivatives (0.2 mmol), and nitroalkane or acetone (0.5 mL) were added. Then the tube was filled up with molecular oxygen and stoppered. The reaction mixture was stirred at 100 ˚C (temperature of oil bath) for 24 h. The Fe3O4 nanoparticles were adsorbed on the magnetic stirring bar when the stirring was stopped. After cooled to r.t., the reaction solution was filtered through Celite in a pipette eluting with EtOAc. The volatile was removed in vacuo, and the residue was purified by column chromatography on silica gel (eluent: hexane-EtOAc = 5:1) to give the corresponding product. Fe3O4 nanoparticles were washed with EtOAc, air-dried, and used directly for the next round of reaction without further purification.
2-(3-Methoxyphenyl)-1,2,3,4-tetrahydroisoquinoline (1e) White solid. Isolated by flash column chromatography (hexane-EtOAc = 5:1, R f  = 0.7). ¹H NMR (400 MHz): δ = 7.26-7.15 (m, 5 H), 6.62-6.60 (m, 1 H), 6.53-6.52 (m, 1 H), 6.41-6.39 (m, 1 H), 4.42 (s, 2 H), 3.82 (s, 3 H), 3.57 (t, J = 5.6 Hz, 2 H), 2.99 (t, J = 6.0 Hz, 2 H) ppm. ¹³C NMR (100 MHz): δ = 160.8, 151.9. 134.9, 134.5, 130.0, 128.5, 126.6, 126.4, 126.1, 108.0, 103.3, 101.5, 55.2, 50.6, 46.4, 29.2 ppm. HRMS (APCI): m/z calcd for C16H18NO [M + 1]+: 240.1383; found: 240.1381.
2-(3-Methoxyphenyl)-1-(nitromethyl)-1,2,3,4-tetrahydroisoquinoline (3i) Isolated by flash column chromatography (hexane-EtOAc = 5:1, R f  = 0.4). Light yellow oil. ¹H NMR (400 MHz): δ = 7.28-7.17 (m, 4 H), 7.14-7.12 (m, 1 H), 6.60 (dd, J = 8.4, 2.4 Hz, 1 H), 6.54 (m, 1 H), 6.42 (dd, J = 8.0, 2.0 Hz, 1 H), 5.54 (dd, J = 7.2, 6.8 Hz, 1 H), 4.87 (dd, J = 12.0, 7.2 Hz, 1 H), 4.55 (dd, J = 11.6, 6.8 Hz, 1 H), 3.80 (s, 3 H), 3.66-3.58 (m, 2 H), 3.00 (ddd, J = 16.4, 8.8, 6.4 Hz, 1 H), 2.68 (dt, J = 16.4, 5.2 Hz, 1 H) ppm. ¹³C NMR (100 MHz): δ = 160.9, 149.7, 135.2, 132.9, 130.2, 129.2, 128.2, 127.0, 126.7, 107.5, 104.0, 101.4, 78.8, 58.3, 55.2, 42.1, 26.6 ppm. HRMS (APCI): m/z calcd for C17H19N2O3 [M + 1]+: 299.1390; found: 299.1391.
2-(3-Methoxyphenyl)-1-(1-nitroethyl)-1,2,3,4-tetrahydroisoquinoline (3j) The ratio of isolated diastereomers is 1.7. Isolated by flash column chromatography (hexane-EtOAc = 5:1, R f  = 0.4). Light yellow oil.
Major isomer: ¹H NMR (400 MHz): δ = 5.05 (dq, J = 14.8, 6.4 Hz, 1 H), 3.79 (s, 3 H), 1.55 (d, J = 6.4 Hz, 3 H) ppm. ¹³C NMR (100 MHz): δ = 160.7, 150.2, 134.7, 131.9, 130.0, 128.7, 128.2, 126.6, 107.9, 104.0, 101.8, 85.4, 62.8, 55.2, 42.7, 26.5, 16.3 ppm.
Minor isomer: ¹H NMR (400 MHz): δ = 4.88 (dq, J = 14.8, 6.4 Hz, 1 H), 3.82 (s, 3 H), 1.71 (d, J = 6.8 Hz, 3 H) ppm. ¹³C NMR (100 MHz): δ = 160.8, 150.5, 135.6, 133.8, 130.1, 129.1, 128.3, 127.3, 107.2, 103.1, 101.1, 88.9, 61.2, 55.2, 43.5, 26.9, 17.5 ppm.
Other overlapped peaks: ¹H NMR (400 MHz): δ = 7.27-7.08 (m), 7.01-7.00 (m), 6.62-6.52 (m), 6.40-6.37 (m), 5.25-5.24 (m), 3.85-3.83 (m), 3.58-3.52 (m), 3.52-3.04 (m), 2.96-2.86 (m) ppm. ¹³C NMR (100 MHz): δ = 126.2 ppm. HRMS (APCI): m/z calcd for C18H21N2O3 [M + 1]+: 313.1547; found: 313.1549.
2-(3-Methoxyphenyl)-1-(1-nitropropyl)-1,2,3,4-tetrahydroisoquinoline (3k) The ratio of isolated diastereomers is 1.6. Isolated by flash column chromatography (hexane-EtOAc = 5:1, R f  = 0.4). Light yellow oil.
Major isomer: ¹H NMR (400 MHz): δ = 5.12 (d, J = 9.6 Hz, 1 H), 4.86 (m, 1 H), 3.77 (s, 3 H) ppm. ¹³C NMR (100 MHz): δ = 160.5, 150.3, 135.5, 133.8, 130.1, 129.3, 128.5, 128.2, 125.9, 108.3, 103.9, 102.2, 92.9, 62.2, 55.2, 42.3, 25.8, 24.5 ppm.
Minor isomer: ¹H NMR (400 MHz): δ = 5.22 (d, J = 9.2 Hz, 1 H), 4.67 (m, 1 H), 3.81 (s, 3 H) ppm. ¹³C NMR (100 MHz): δ = 160.7, 150.3, 134.6, 132.1, 129.8, 128.6, 128.2, 127.2, 126.6, 106.8, 102.8, 100.8, 96.1, 60.7, 55.1, 43.5, 26.9, 25.0 ppm.
Other overlapped peaks: ¹H NMR (400 MHz): δ = 7.26-7.08 (m), 7.01-7.18 (m), 7.00-6.98 (m), 6.62-6.52 (m), 6.40-6.35 (m), 3.87-3.47 (m), 3.12-3.06 (m), 2.93-2.85 (m), 2.26-2.06 (m), 1.86-1.78 (m), 0.96-0.92 (m) ppm. ¹³C NMR (100 MHz): δ = 10.6 ppm. HRMS (APCI): m/z calcd for C19H23N2O3 [M + 1]+: 327.1703; found: 327.1703.