PDF herunterladen
Synlett 2012(5): 741-746  
DOI: 10.1055/s-0031-1290358
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

2-(Diphenylphosphino)benzoyl-Substituted Calix[4]arene: Efficient Organocatalyst in Aza-Morita-Baylis-Hillman Reaction of N-Sulfonated Imines with Methyl Vinyl Ketone

Yanyan Shen, Qian Tang, Chenchen Zhang, Weihui Zhong*
Key Laboratory of Pharmaceutical Engineering of Ministry of Education, College of Pharmaceutical Sciences, Zhejiang University of Technology, Hangzhou 310014, P. R. of China
Fax: +86(571)88871087; e-Mail: weihuizhong@zjut.edu.cn;
Weitere Informationen

Publikationsverlauf

Received 16 October 2011
Publikationsdatum:
24. Februar 2012 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

A novel bifunctional organocatalyst 5,11,17,23-tetra­butyl-25-[2-(diphenylphosphino)benzoate]-26,27,28-trihydroxycalix-[4]arene (LB3) was synthesized and applied to promote the aza-Morita-Baylis-Hillman (aza-MBH) reaction of N-sulfonated im­ines with methyl vinyl ketone. It was found that in the presence of acidic additives the reaction rate could be accelerated to give aza-MBH adducts in good to excellent yields. Compared to our previous phosphine-containing calix[4]arene LB1, the novel catalyst was more effective.

Key word

phosphine-containing calix[4]arene - organocatalysis - aza-Morita-Baylis-Hillman

    References and Notes

  • 1a Perlmutter P. Teo CC. Tetrahedron Lett.  1984,  25:  5951 
    Google Scholar
  • 1b Ciganek E. Org. React. (N. Y.)  1997,  51:  201 
    Google Scholar
  • 1c Basavaiah D. Rao PD. Hyma RS. Tetrahedron  1996,  52:  8001 
    Google Scholar
  • 1d Basavaiah D. Rao AJ. Satyanarayana T. Chem. Rev.  2003,  103:  811 
    Google Scholar
  • 1e Basavaiah D. Rao KV. Reddy RJ. Chem. Soc. Rev.  2007,  36:  1581 
    Google Scholar
  • 1f Declerck V. Martinez J. Lamaty F. Chem. Rev.  2009,  109:  1 
    Google Scholar
  • 2a Drewes SE. Ross GHP. Tetrahedron  1988,  44:  4653 
    Google Scholar
  • 2b Trost BM. Science  1991,  254:  1471 
    Google Scholar
  • 2c Trost BM. Acc. Chem. Res.  2002,  35:  695 
    Google Scholar
  • 2d Basavaiah D. Reddy BS. Badsara SS. Chem. Rev.  2010,  110:  5447 
    Google Scholar
  • 3a Shi M. Xu YM. Angew. Chem. Int. Ed.  2002,  41:  4507 
    Google Scholar
  • 3b Shi M. Chen LH. Chem. Commun.  2003,  1310 
    Google Scholar
  • 3c Kawahara S. Nakano A. Esumi T. Iwabuchi Y. Hatakeyama S. Org. Lett.  2003,  5:  3103 
    Google Scholar
  • 3d Balan D. Adolfsson H. Tetrahedron Lett.  2003,  44:  2521 
    Google Scholar
  • 3e Masson G. Housseman C. Zhu J. Angew. Chem. Int. Ed.  2007,  46:  4614 
    Google Scholar
  • 3f Abermil N. Masson G. Zhu J. J. Am. Chem. Soc.  2008,  130:  12596 
    Google Scholar
  • 3g Meng X. Huang Y. Chen R. Chem. Eur. J.  2008,  14:  6852 
    Google Scholar
  • 3h Liu YH. Shi M. Adv. Synth. Catal.  2008,  350:  122 
    Google Scholar
  • 4a Iwabuchi Y. Nakatani M. Yodoyama N. Hatakeyama S. J. Am. Chem. Soc.  1999,  121:  10219 
    Google Scholar
  • 4b Nakano A. Ushiyama M. Iwabuchi Y. Hatakeyama S. Adv. Synth. Catal.  2005,  347:  1790 
    Google Scholar
  • 4c Shi M. Xu YM. Shi YL. Chem. Eur. J.  2005,  11:  1794 
    Google Scholar
  • 4d Nakano A. Takahashi K. Ishihara J. Hatakeyama S. Org. Lett.  2006,  8:  5357 
    Google Scholar
  • 4e McDougal NT. Schaus SE. J. Am. Chem. Soc.  2003,  125:  12094 
    Google Scholar
  • 4f Matsui K. Takizawa S. Sasai H. Synlett  2006,  761 
    Google Scholar
  • 4g Liu YH. Chen LH. Shi M. Adv. Synth. Catal.  2006,  348:  973 
    Google Scholar
  • 4h Jiang YQ. Shi YL. Shi M. J. Am. Chem. Soc.  2008,  130:  7202 
    Google Scholar
  • 4i Utsumi N. Zhang H. Tanaka F. Barbas CF. Angew. Chem. Int. Ed.  2007,  46:  1878 
    Google Scholar
  • 4j Sohtome Y. Tanatani A. Hashimoto Y. Nagasawa K. Tetrahedron Lett.  2004,  45:  5589 
    Google Scholar
  • 4k Berkessel A. Roland K. Neudörfl JM. Org. Lett.  2006,  8:  4195 
    Google Scholar
  • 4l Shi M. Liu XG. Org. Lett.  2008,  10:  1043 
    Google Scholar
  • 4m Wang J. Yu X. Zu L. Wang W. Org. Lett.  2005,  7:  4293 
    Google Scholar
  • 4n Shi YL. Shi M. Adv. Synth. Catal.  2007,  349:  2129 
    Google Scholar
  • 4o Yuan K. Zhang L. Song HL. Hu YJ. Wu XY. Tetrahedron Lett.  2008,  49:  6262 
    Google Scholar
  • 5a Kuhn P. Jeunesse C. Matt D. Harrowfield J. Ricard L. Dalton Trans.  2006,  28:  3454 
    Google Scholar
  • 5b Chawla HM. Singh SP. Tetrahedron  2008,  64:  741 
    Google Scholar
  • 5c Tashev E. Tosheva T. Shenkov S. Chauvin AS. Lachkova V. Petrova R. Scopelliti R. Varbanov S. Supramol. Chem.  2007,  19:  447 
    Google Scholar
  • 6 Zhong WH. Zheng YM. Zhou JD. Shen YY. Synlett  2010,  3057 
    Google Scholar
  • 7a Auge J. Lubin N. Lubineau A. Tetrahedron Lett.  1994,  35:  7947 
    Google Scholar
  • 7b Yamada YMA. Ikegami S. Tetrahedron Lett.  2000,  41:  2165 
    Google Scholar
  • 7c Yu C. Liu B. Hu L. J. Org. Chem.  2001,  66:  5413 
    Google Scholar
  • 7d Cai J. Zhou Z. Zhao G. Tang C. Org. Lett.  2002,  4:  4723 
    Google Scholar
  • 7e Aggarwal VK. Dean DK. Mereu A. Williams R. J. Org. Chem.  2002,  67:  510 
    Google Scholar
  • 7f Garnier GM. Liu F. Org. Biomol. Chem.  2009,  7:  1272 
    Google Scholar
  • 8a Buskens P. Klankermayer J. Leitner W. J. Am. Chem. Soc.  2005,  127:  16762 
    Google Scholar
  • 8b Matsui K. Takizawa S. Sasai H. J. Am. Chem. Soc.  2005,  127:  3680 
    Google Scholar
  • 8c Shi M. Chen LH. Li CQ. J. Am. Chem. Soc.  2005,  127:  3790 
    Google Scholar
  • 8d Matsui K. Tanaka K. Horii A. Takizawa S. Sasai H. Tetrahedron: Asymmetry  2006,  17:  578 
    Google Scholar
  • 8e Garnier JM. Anstiss C. Liu F. Adv. Synth. Catal.  2009,  351:  331 
    Google Scholar
  • 8f Takizawa S. Inoue N. Hirata S. Sasai H. Angew. Chem. Int. Ed.  2010,  49:  9725 
    Google Scholar
  • 8g Wei Y. Shi M. Acc. Chem. Res.  2010,  43:  1005 
    Google Scholar
  • 8h Zhong F. Wang Y. Han X. Huang K. Lu Y. Org. Lett.  2011,  13:  1310 
    Google Scholar
9

Typical Procedure for the Preparation of LB3: A suspension of para-tert-butylcalix[4]arene (1.30 g, 2.0 mmol) in toluene (45 mL) was cooled to 0 ˚C. Then 2-(diphenylphosphino)benzoic acid (0.92 g, 3.0 mmol), dicyclohexylcarbodiimide (DCC, 0.699 g, 3.4 mmol) and 4-(N,N-dimethylamino)pyridine (DMAP; 0.041 g, 0.34 mmol) were added. After stirring at 60 ˚C for 12 h, the suspension was filtrated and extracted with CH2Cl2 (100 mL) and then washed with H2O (2 × 50 mL). The organic layer was dried with anhyd Na2SO4 and evaporated to afford a white solid that was purified by flash chromatography (EtOAc-PE, 1:30) to afford LB3; yield 60%; mp 181.0-182.1 ˚C. ¹H NMR (400 MHz, CDCl3): δ = 0.88 (s, 15 H, Me), 1.08 (s, 15 H, Me), 1.25 (s, 6 H, Me), 3.72 (m, 8 H, CH2), 6.10 (br, 1 H, OH), 6.49 (br, 2 H, OH), 6.68 (s, 2 H, ArH), 6.88 (s, 1 H, ArH), 7.01 (s, 1 H, ArH), 7.08 (s, 2 H, ArH), 7.17-7.23 (m, 6 H, ArH), 7.29 (t, J = 5.6 Hz, 9 H, ArH), 7.66 (s, 1 H, ArH). ¹³C NMR (100 MHz, CDCl3): δ = 162.1, 148.5, 148.1, 144.0, 143.1, 140.9, 140.6, 138.0, 137.9, 137.6, 137.5, 134.1 (2 × C), 133.9, 133.8, 133.5, 133.4, 132.9 (2 × C), 131.9 (2 × C), 131.6 (2 × C), 131.0, 130.8, 128.4 (2 × C), 128.3 (3 × C), 128.2 (4 × C), 126.8 (2 × C), 126.1 (2 × C), 125.9, 125.7, 125.3, 124.9, 124.8, 34.0, 33.9, 31.6 (9 × C), 31.3 (2 × C), 31.2 (2 × C), 31.1 (4 × C), 29.8. MS (ESI): m/z = 936.6 [M - 1]-. HRMS (ESI): m/z [M - 1]- calcd for C63H69O5P: 936.4883; found: 935.4756.

10

Typical Procedure for the Aza-Morita-Baylis-Hillman Reaction of N-Sulfonated Imines 1 with MVK in the Presence of LB3 (10 mol%): To N-(2-fluorobenzylidene)-4-methylbenzenesulfonamide (1a; 0.259 g, 1.0 mmol), LB3 (0.094 g, 0.10 mmol) and PhCO2H (0.012 g, 0.10 mmol) in CH2Cl2 (3.0 mL) was added MVK (0.105 g, 1.5 mmol) at r.t. Then the temperature was raised to 40 ˚C with stirring for 4 h. The solution was extracted with CH2Cl2 (20 mL) and then washed with H2O (2 × 15 mL). The organic layer was dried with Na2SO4 and evaporated to afford a white solid that was purified by flash chromatography (eluent: EtOAc-PE, 1:4) to give the corresponding aza-Morita-Baylis-Hillman adduct 3a (0.289 g, 88%); mp 120.2-121.3 ˚C (lit.,³g 120-121 ˚C). ¹H NMR (400 MHz, CDCl3): δ = 2.15 (s, 3 H, Me), 2.42 (s, 3 H, Me), 5.27 (d, J = 8.7 Hz, 1 H, CH2), 5.71 (d, J = 8.7 Hz, 1 H, CH2), 6.07 (s, 1 H, CH), 6.09 (s, 1 H, NH), 7.08 (m, 2 H, ArH), 7.17-7.22 (m, 5 H, ArH), 7.64 (d, J = 8.0 Hz, 2 H, ArH). MS (ESI): m/z = 328.2 [M - 1]-.