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Synlett 2011(4): 495-498  
DOI: 10.1055/s-0030-1259512
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© Georg Thieme Verlag Stuttgart ˙ New York

Chiral Zwitterions from Vicinal Diamines: Effective and Recoverable Asymmetric Enamine Catalysts

Yupu Qiao, Long Zhang, Sanzhong Luo*, Jin-Pei Cheng
Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. of China
Fax: +86(10)62554446; e-Mail: luosz@iccas.ac.cn;
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Publication History

Received 28 October 2010
Publication Date:
27 January 2011 (online)

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Abstract

A series of chiral zwitterionic vicinal diamines were designed and synthesized. The zwitterionic catalysts demonstrated good reactivity and enantioselectivity in asymmetric enamine-based transformations and could be readily recycled and reused for four times.

Key words

chiral zwitterion - organocatalysts - enamine - catalyst immobilization

    References and Notes

  • 1a Berkessel A. Groger H. Asymmetric Organocatalysis   Wiley-VCH; Weinheim: 2005. 
    Google Scholar
  • 1b Dalko PI. Enantioselective Organocatalysis   Wiley-VCH; Weinheim: 2007. 
    Google Scholar
  • 1c Dalko PI. Moisan L. Angew. Chem. Int. Ed.  2004,  43:  5138 
    Google Scholar
  • 1d Saito S. Yamamoto H. Acc. Chem. Res.  2004,  37:  570 
    Google Scholar
  • 1e Notz W. Tanaka F. Barbas CF. Acc. Chem. Res.  2004,  37:  580 
    Google Scholar
  • 1f Mukherjee S. Yang JW. Hoffmann S. List B. Chem. Rev.  2007,  107:  5471 
    Google Scholar
  • For recent examples, see:
  • 2a Luo SZ. Xu H. Li J. Zhang L. Cheng J.-P. J. Am. Chem. Soc.  2007,  129:  3074 
    Google Scholar
  • 2b Chen W. Du W. Duan Y.-Z. Wu Y. Yang S.-Y. Chen Y.-C. Angew. Chem. Int. Ed.  2007,  46:  7667 
    Google Scholar
  • 2c Kano T. Tanaka Y. Osawa K. Yurino T. Maruoka KJ. Chem. Commun.  2009,  1956 
    Google Scholar
  • 2d Yang Y.-Q. Chen X.-K. Xiao H. Liu W. Zhao G. Chem. Commun.  2010,  46:  4130 
    Google Scholar
  • 2e Liu C. Lu Y. Org. Lett.  2010,  12:  2278 
    Google Scholar
  • 2f Luo SZ. Qiao YP. Zhang L. Li J. Li X. Cheng J.-P. J. Org. Chem.  2009,  74:  9521 
    Google Scholar
  • 2g Li J. Fu NK. Li X. Luo SZ. Cheng J.-P. J. Org. Chem.  2010,  75:  4501 
    Google Scholar
  • 2h Hu SS. Li J. Xiang J. Pan J. Luo SZ. Cheng J.-P. J. Am. Chem. Soc.  2010,  132:  7216 
    Google Scholar
  • 2i Luo SZ. Zhou P. Li J. Cheng J.-P. Chem. Eur. J.  2010,  16:  4457 
    Google Scholar
  • 2j For a review, see: Xu L.-W. Luo J. Lu Y. Chem. Commun.  2009,  1807 
    Google Scholar
  • 3 For a review, see: Luo SZ. Zhang L. Cheng J.-P. Chem. Asian J.  2009,  4:  1184 
    CrossrefGoogle Scholar
  • 4 Zhang L. Luo SZ. Mi XL. Liu S. Qiao YP. Xu H. Cheng J.-P. Org. Biomol. Chem.  2008,  6:  567 
    CrossrefGoogle Scholar
  • 7a Mase N. Thayumanavan R. Tanaka F. Barbas CF. Org. Lett.  2004,  6:  2527 
    Google Scholar
  • 7b Wang W. Wang J. Li H. Angew. Chem Int Ed.  2005,  44:  1369 
    Google Scholar
  • 7c Mase N. Watanabe K. Yoda H. Takabe K. Tanaka F. Barbas CF. J. Am. Chem. Soc.  2006,  128:  4966 
    Google Scholar
  • 7d Lalonde MP. Chen YG. Jacobsen EN. Angew. Chem. Int. Ed.  2006,  45:  6366 
    Google Scholar
  • 7e Sato A. Yoshida M. Hara S. Chem. Commun.  2008,  46:  6242 
    Google Scholar
  • 7f Zhang X.-J. Liu S.-P. Li X.-M. Yan M. Chan Albert SC. Chem. Commun.  2009,  7:  833 
    Google Scholar
  • 7g Yoshida M. Sato A. Hara S. Org. Biomol. Chem.  2010,  8:  3031 
    Google Scholar
  • 7h Xiao J. Xu F.-X. Lu Y.-P. Loh T.-P. Org. Lett.  2010,  12:  1220 
    Google Scholar
  • 7i Chen J.-R. Cao Y.-J. Zou Y.-Q. Tan F. Fu L. Zhu X.-Y. Xiao W.-J. Org. Biomol. Chem.  2010,  8:  1275 
    Google Scholar
  • 7j He TX. Gu Q. Wu X.-Y. Tetrahedron  2010,  66:  3195 
    Google Scholar
  • 7k Bai J.-F. Xu X.-Y. Huang Q.-C. Peng L. Wang L.-X. Tetrahedron Lett.  2010,  51:  2803 
    Google Scholar
  • 8a Nakadai M. Saito S. Yamamoto H. Tetrahedron  2002,  58:  8167 
    Google Scholar
  • 8b Luo SZ. Li J. Zhang L. Xu H. Cheng J.-P. Chem. Eur. J.  2008,  14:  1273 
    Google Scholar
  • 8c Luo SZ. Li J. Xu H. Zhang L. Cheng J.-P. Org. Lett.  2007,  9:  3675 
    Google Scholar
5

Spectral Data for Catalyst 3a ¹H NMR (300 MHz, D2O): δ = 7.93-7.95 (m, 1 H), 7.63-7.66 (m, 2 H), 7.48-7.51 (m, 1 H), 3.78-3.91 (m, 2 H), 3.65-3.70 (m, 1 H), 3.33-3.48 (m, 2 H), 2.04-2.23 (m, 3 H), 1.82-1.89 (m, 1 H). ¹³C NMR (75 MHz, D2O): δ = 172.5, 139.5, 133.1, 131.6, 127.8, 127.2, 60.6, 45.4, 39.8, 26.8, 22.6. IR (neat): 3403, 3077, 2977, 2886, 1637, 1595, 1566, 1531, 1431, 1316, 1234, 1170, 1143, 1085, 1018, 833, 767, 731 cm-¹. HRMS: m/z calcd for C12H16N2O4S [M + H]+: 285.0904; found: 285.0902. [α]D ²0 +32.2 (c 0.5, MeOH).
Compound 3b: ¹H NMR (300 MHz, D2O): δ = 3.72 (br s, 1 H), 3.33 (br s, 2 H), 2.82-2.97 (br, 6 H), 2.22 (s, 1 H), 1.97-2.06 (m, 4 H), 1.73 (s, 1 H). ¹³C NMR (75 MHz, D2O): δ = 59.0, 49.3, 48.8, 47.1, 45.5, 28.1, 23.6, 23.1. IR (neat): 3422, 2964, 2866, 1644, 1461, 1419, 1186, 1042 cm-¹. HRMS:
m/z calcd for C8H18N2O3S [M + H]+: 223.1111; found: 223.1109. [α]D ²0 +32.2 (c 0.5, MeOH).
Compound 3c: ¹H NMR (300 MHz, D2O): δ = 3.80-3.84 (t, J = 6.6 Hz, 1 H), 3.37-3.41 (br, 2 H), 2.91-2.96 (br, 3 H), 2.62-2.75 (m, 4 H), 2.35 (br s, 2 H), 2.02-2.23 (m, 4 H), 1.94 (br s, 2 H), 1.75 (br, 7 H), 1.53 (br s, 1 H), 1.26-1.28 (br, 4 H), 0.91-0.94 (br, 2 H). ¹³C NMR (75 MHz, D2O): δ = 60.9, 57.9, 55.7, 52.5, 48.9, 45.2, 35.3, 31.6, 28.0, 26.6, 25.9, 25.8, 22.9, 21.3. IR (neat): 3444, 2923, 2850, 1644, 1453, 1203, 1042 cm-¹. HRMS: m/z calcd for C15H30N2O3S [M + H]+: 319.2050; found: 319.2049. [α]D ²0 +33.8 (c 0.5, MeOH).
Compound 3d: ¹H NMR (300 MHz, D2O): δ = 3.80-3.82 (m, 1 H), 3.37-3.42 (t, J = 7.2 Hz, 2 H), 2.92-2.97 (m, 3 H), 2.71-2.78 (m, 4 H), 2.37 (s, 2 H), 2.04-2.25 (m, 3 H), 1.95-1.97 (m, 2 H), 1.76-1.82 (m, 1 H), 0.95 (s, 9 H). ¹³C NMR (D2O, 75 MHz): δ = 66.7, 58.1, 57.0, 54.7, 49.0, 45.1, 32.1, 28.0, 27.8, 22.8, 21.4. IR (neat): 3446, 2953, 2867, 2828, 1644, 1481, 1464, 1394, 1361, 1186, 1042 cm-¹. HRMS: m/z calcd for C13H28N2O3S [M + H]+: 293.1893; found: 293.1891. [α]D ²0 +16.8 (c 0.5, MeOH).
Compound 3e: ¹H NMR (300 MHz, D2O): δ = 3.84 (s, 1 H), 3.33-3.38 (t, J = 6.6 Hz, 2 H), 2.66-3.03 (m, 7 H), 1.96-2.26 (m, 5 H), 1.71-1.77 (m, 1 H), 1.57-1.61 (m, 1 H), 1.40-1.42 (m, 1 H), 0.92-0.94 (d, J = 6 Hz, 6 H). ¹³C NMR (75 MHz, D2O): δ = 57.5, 54.7, 51.6, 51.4, 48.7, 45.2, 33.8, 28.2, 26.0, 23.0, 22.0, 21.9, 20.8. IR (neat): 3460, 2957, 2871, 1651, 1467, 1384, 1368, 1196, 1042 cm-¹. HRMS: m/z calcd for C13H28N2O3S [M + H]+: 293.1893; found: 293.1882.
[α]D ²0 +12.2 (c 0.5, MeOH).
Compound 7: ¹H NMR (300 MHz, D2O): δ = 3.09-3.14 (m, 1 H), 2.94-3.03 (br s, 2 H), 2.51-2.79 (m, 4 H), 2.16-2.20 (d, J = 11.4 Hz, 1 H), 1.80-2.00 (m, 5 H), 1.57-1.63 (m, 1 H), 1.33-1.44 (m, 6 H), 0.92-0.96 (q, J = 3.6, 6.3 Hz,). ¹³C NMR (75 MHz, D2O): δ = 62.7, 50.9, 48.8, 48.2, 47.8, 36.9, 30.2, 25.9, 24.6, 23.8, 23.2, 23.0, 22.3, 21.8. IR (neat): 3483, 3447, 2951, 2867, 1637, 1468, 1383, 1367, 1207, 1183, 1043 cm-¹. HRMS: m/z calcd for C14H30N2NaO3S [M + Na]+: 329.1869; found: 329.1868. [α]D ²0 +59.4 (c 0.5, MeOH).

6

Upon long-term storage (>3 months), the solid becomes syrup due to the absorption of moisture. This syrup can be restored to solid power after dried under vaccum.