Download PDF
Synlett 2009(10): 1667-1669  
DOI: 10.1055/s-0029-1217191
CLUSTER
© Georg Thieme Verlag Stuttgart ˙ New York

One-Pot Preparation of Chiral Dinuclear Vanadium(V) Complex

Shinobu Takizawa, Doss Rajesh, Tomomi Katayama, Hiroaki Sasai*
The Institute of Scientific and Industrial Research (ISIR), Osaka University, Mihogaoka, Ibaraki-shi, Osaka 567-0047, Japan
Fax: +81(6)68798469; e-Mail: sasai@sanken.osaka-u.ac.jp;
Further Information

Publication History

Received 16 February 2009
Publication Date:
02 June 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

A convenient one-pot procedure for the preparation of dinuclear vanadium(V) complex is described. The complex exhibited high catalytic activity for oxidative coupling of 2-naphthol derivatives. In addition, coupling of 9-phenanthrol gave (S)-10,10′-dihydroxy-9,9′-biphenanthryl in quantitative yield with 93% ee.

Key words

oxidative coupling - dinuclear vanadium complex - dual activation - biphenanthrol - asymmetric synthesis

    References and Notes

  • 1a Brunel JM. Chem. Rev.  2005,  105:  857 
    Google Scholar
  • 1b Love BE. Curr. Org. Synth.  2006,  3:  169 
    Google Scholar
  • 2a Smrcina M. Poláková J. Vyskocil S. Kočovský P.
    J. Org. Chem.  1993,  58:  4534 
    Google Scholar
  • 2b Sridhar M. Vadivel SK. Bhalerao UT. Tetrahedron Lett.  1997,  38:  5695 
    Google Scholar
  • 2c Nakajima M. Miyoshi I. Kanayama K. Hashimoto S. Noji M. Koga K. J. Org. Chem.  1999,  64:  2264 
    Google Scholar
  • 2d Irie R. Matsutani K. Katsuki T. Synlett  2000,  1433 
    Google Scholar
  • 2e Irie R. Katsuki T. Chem. Rec.  2004,  4:  96 
    Google Scholar
  • 2f Li X. Yang J. Kozlowski MC. Org. Lett.  2001,  3:  1137 
    Google Scholar
  • 2g Kozlowski MC. Li X. Carroll PJ. Xu Z. Organometallics  2002,  21:  4513 
    Google Scholar
  • 2h Xie X. Phuan P.-W. Kozlowski MC. Angew. Chem. Int. Ed.  2003,  42:  2168 
    Google Scholar
  • 2i Li X. Hewgley JB. Mulrooney CA. Yang J. Kozlowski MS. J. Org. Chem.  2003,  68:  5500 
    Google Scholar
  • 2j Mulrooney CA. Li X. DiVirgilio ES. Kozlowski MC. J. Am. Chem. Soc.  2003,  125:  6856 
    Google Scholar
  • 2k Kim KH. Lee D.-W. Lee Y.-S. Ko D.-H. Ha D.-C. Tetrahedron  2004,  60:  9037 
    Google Scholar
  • 2l Illesinghe J. Ebeling R. Ferguson B. Patel J. Campi EM. Jackson WR. Robinson AJ. Aust. J. Chem.  2004,  57:  167 
    Google Scholar
  • 2m Temma T. Habaue S. Tetrahedron Lett.  2005,  46:  5655 
    Google Scholar
  • 2n Temma T. Habaue S. J. Polym. Sci., Part A: Polym. Chem.  2005,  43:  6287 
    Google Scholar
  • 2o Temma T. Hatano B. Habaue S. Tetrahedron  2006,  62:  8559 
    Google Scholar
  • 2p Temma T. Hatano B. Habaue S. Polymer  2006,  47:  1845 
    Google Scholar
  • 2q Temma T. Takahashi Y. Yoshii Y. Habaue S. Polymer J.  2007,  39:  524 
    Google Scholar
  • 2r Morgan BJ. Xie X. Phuan P.-W. Kozlowski MC. J. Org. Chem.  2007,  72:  6171 
    Google Scholar
  • 2s Kozlowski MC. Dugan EC. DiVirgilio ES. Maksimenka K. Bringmann G. Adv. Synth. Catal.  2007,  349:  583 
    Google Scholar
  • 3a Hon S.-W. Li C.-H. Kuo J.-H. Barhate NB. Liu Y.-H. Wang Y. Chen C.-T. Org. Lett.  2001,  3:  869 
    Google Scholar
  • 3b Chu C.-Y. Hwang D.-R. Wang S.-K. Uang B.-J. Chem. Commun.  2001,  980 
    Google Scholar
  • 3c Barhate NB. Chen C.-T. Org. Lett.  2002,  4:  2529 
    Google Scholar
  • 3d Luo Z. Liu Q. Gong L. Cui X. Mi A. Jiang Y. Chem. Commun.  2002,  914 
    Google Scholar
  • 3e Luo Z. Liu Q. Gong L. Cui X. Mi A. Jiang Y. Angew. Chem. Int. Ed.  2002,  41:  4532 
    Google Scholar
  • 3f Chu C.-Y. Uang B.-J. Tetrahedron: Asymmetry  2003,  14:  53 
    Google Scholar
  • 3g Somei H. Asano Y. Yoshida T. Takizawa S. Yamataka H. Sasai H. Tetrahedron Lett.  2004,  45:  1841 
    Google Scholar
  • 3h Tada M. Taniike T. Kantam LK. Iwasawa Y. Chem. Comunn.  2004,  2542 
    Google Scholar
  • 3i Tada M. Kojima N. Izumi Y. Taniike T. Iwasawa Y. J. Phys. Chem. B  2005,  109:  9905 
    Google Scholar
  • 3j Habaue S. Murakami S. Higashimura H. J. Polym. Sci., Part A: Polym. Chem.  2005,  43:  5872 
    Google Scholar
  • 3k Tada M. Iwasawa Y. Chem. Comunn.  2006,  2833 
    Google Scholar
  • 3l Guo Q.-X. Wu Z.-J. Luo Z.-B. Liu Q.-Z. Ye J.-L. Luo S.-W. Cun L.-F. Gong L.-Z. J. Am. Chem. Soc.  2007,  129:  13927 
    Google Scholar
  • 4a Takizawa S. Katayama T. Kameyama C. Onitsuka K. Suzuki T. Yanagida T. Kawai T. Sasai H. Chem. Commun.  2008,  1810 
    Google Scholar
  • 4b Takizawa S. Katayama T. Somei H. Asano Y. Yoshida T. Kameyama C. Rajesh D. Onitsuka K. Suzuki T. Mikami M. Yamataka H. Jayaprakash D. Sasai H. Tetrahedron  2008,  64:  3361 
    Google Scholar
  • 4c Takizawa S. Katayama T. Sasai H. Chem. Commun.  2008,  4113 
    Google Scholar
  • 5 Pawar VD. Bettigeri S. Weng S.-S. Kao J.-Q. Chen C.-T. J. Am. Chem. Soc.  2006,  128:  6308 
    CrossrefGoogle Scholar
  • 8a Yamamoto K. Fukushima H. Nakazaki M. J. Chem. Soc., Chem. Commun.  1984,  1490 
    Google Scholar
  • 8b Escher IH. Pfaltz A. Tetrahedron  2000,  56:  2879 
    Google Scholar
  • 8c Aydin J. Kumar KS. Sayah MJ. Wallner OA. Szabó KJ. J. Org. Chem.  2007,  72:  4689 
    Google Scholar
  • 8d Lin S.-Z. You T.-P. Tetrahedron  2009,  65:  1010 
    Google Scholar
  • 9a Toda F. Tanaka K. Stein Z. Goldberg I. J. Org. Chem.  1994,  59:  5748 
    Google Scholar
  • 9b Lin Y. Chien L.-C. Tetrahedron: Asymmetry  1998,  9:  63 
    Google Scholar
  • 10 Fu J.-M. Snieckus V. Can. J. Chem.  2000,  78:  905 
    CrossrefGoogle Scholar
6

General Procedure for the One-Pot Preparation of (R a , S , S)-1
A round-bottomed flask was charged with (R)-3,3′-diformyl-2,2′-dihydroxy-1,1′-binaphthyl (2, 500 mg,
1.46 mmol), (S)-tert-leucine (3, 383 mg, 2.92 mmol), VOSO4˙H2O (952 mg, 5.84 mmol), MS 3 Å (1.46 g) and MeOH (50 mL) under O2 (balloon). The reaction mixture was refluxed, and the consumption of 2 was monitored by TLC (acetone-hexane, 1:3). The resulting solution was gradually cooled down to r.t. and filtered through Celite to remove MS 3 Å. The filtrate was evaporated, and the resulting black solid was dissolved in CH2Cl2 and washed with H2O. The organic phase was dried over anhyd Na2SO4 and concentrated in vacuum to give (R a ,S,S)-1 (738 mg, 69%) as a black powder. Compound (R a ,S,S)-1: ¹H NMR (270 MHz, CD3OD): δ = 8.96 (s, 2 H, CH=N), 8.48 (s, 2 H, ArH), 8.06 (t, J = 4.7 Hz, 2 H, ArH), 7.70 (t, J = 4.9 Hz, 2 H, ArH), 7.44-7.38 (m, 4 H, ArH), 4.23 (s, 2 H, CHt-Bu), 1.25 (s, 18 H, t-Bu). ¹³C NMR (67.7 MHz, CD3OD): δ = 167.9, 138.7, 137.6, 130.6, 130.5, 129.6, 127.4, 125.3, 124.1, 83.8, 38.8, 28.2. 5¹V NMR (CD3OD): δ = -557.2. IR: 3436 (OH), 1683 (C=N), 1608 (C=O), 996 (V=O) cm-¹. HRMS-FAB: m/z calcd for C34H35N2O10V2: 733.1171 [M + H]+; found: 733.1185.

7

The catalyst 1 prepared by the two-step promoted coupling reaction of 2-naphthol to afford (S)-BINOL with 96% yield and 85% ee in 24 h at r.t. under air.

11

Representative Procedure for the Oxidative Coupling of 9-Phenanthrol Using ( R a , S , S )-1 In a round-bottomed flask (500 mL) was taken CH2Cl2 (240 mL) and 9-phenanthrol (5, 6.0 g, 30.9 mmol). Compound (R a ,S,S)-1 (1.1 g, 1.54 mmol) was charged, and the reaction vessel was purged with O2 (balloon). The reaction was stirred for 48 h at -10 ˚C. A short column to remove the catalyst gave (S)-4 in quantitative yield with 90% ee. Single recrystallization of the product thus obtained with hexane-acetone (5:4) gave optically pure (S)-4 in 79% yield.
Compound (S)-4: >99% ee, [α]D ²³ -65.7 (c 1.2, CHCl3).