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Synlett 2004(13): 2434-2436  
DOI: 10.1055/s-2004-832821
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© Georg Thieme Verlag Stuttgart · New York

Catalytic Asymmetric Cyano-Phosphorylation of Aldehydes Promoted by Heterobimetallic YLi3tris(binaphthoxide) (YLB) Complex

Yumi Abiko, Noriyuki Yamagiwa, Mari Sugita, Jun Tian, Shigeki Matsunaga, Masakatsu Shibasaki*
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Fax: +81(3)56845206; e-Mail: mshibasa@mol.f.u-tokyo.ac.jp;
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Publication History

Received 2 June 2004
Publication Date:
24 September 2004 (online)

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Abstract

A highly enantioselective cyano-phosphorylation of aldehydes catalyzed by YLi3tris(binaphthoxide) complex (YLB, 1) is described. Slow addition of diethyl cyanophosphonate (4) to aldehydes 5 in the presence of 1 (10 mol%), H2O (30 mol%), tris(2,6-dimethoxyphenyl)phosphine oxide (10 mol%, 3a), and BuLi (10 mol%) afforded cyanohydrin O-phosphates 6 in up to 98% yield and 97% ee.

Key words

asymmetric catalysis - cyanohydrins - Lewis acid - phosphorylation - yttrium

    References

  • For recent reviews for catalytic asymmetric cyanation reaction of carbonyl compounds, see:
  • 1a Brunel JM. Holmes IP. Angew. Chem. Int. Ed.  2004,  43:  2752 
    Google Scholar
  • 1b North M. Tetrahedron: Asymmetry  2003,  14:  147 
    Google Scholar
  • 1c Shibasaki M. Kanai M. Funabashi K. Chem. Commun.  2002,  1989 
    Google Scholar
  • 1d Gröger H. Chem.-Eur. J.  2001,  7:  5246 
    Google Scholar
  • 1e Shibasaki M. Kanai M. Chem. Pharm. Bull.  2001,  49:  511 
    Google Scholar
  • 1f Gregory RJH. Chem. Rev.  1999,  99:  3949 
    Google Scholar
  • 2a Tian J. Yamagiwa N. Matsunaga S. Shibasaki M. Angew. Chem. Int. Ed.  2002,  41:  3636 
    CrossrefGoogle Scholar
  • 2b Tian J. Yamagiwa N. Matsunaga S. Shibasaki M. Org. Lett.  2003,  5:  3021 
    CrossrefGoogle Scholar
  • 2c For other catalytic asymmetric reaction using YLB(1) complex, see: Yamagiwa N. Matsunaga S. Shibasaki M. J. Am. Chem. Soc.  2003,  125:  16178 
    CrossrefGoogle Scholar
  • 3a Casas J. Baeza A. Sansano JM. Nájera C. Saá JM. Tetrahedron: Asymmetry  2003,  14:  197 
    CrossrefGoogle Scholar
  • 3b Belokon’ YN. Blacker AJ. Clutterbuck LA. North M. Org. Lett.  2003,  5:  4505 
    CrossrefGoogle Scholar
  • 4 Tian S.-K. Deng L. J. Am. Chem. Soc.  2001,  123:  6195 
    CrossrefPubMedGoogle Scholar
  • For reviews on lanthanide heterobimetallic asymmetric catalysis, see
  • 5a Shibasaki M. Yoshikawa N. Chem. Rev.  2002,  102:  2187 
    CrossrefGoogle Scholar
  • 5b Shibasaki M. Sasai H. Arai T. Angew. Chem., Int. Ed. Engl.  1997,  36:  1236 
    CrossrefGoogle Scholar
  • 5c For the preparation and property of YLB complex: Aspinall HC. Dwyer JLM. Greeves N. Steiner A. Organometallics  1999,  18:  1366 
    CrossrefGoogle Scholar
  • 6 Hodakowski JE. Mohammed AH. Eur. Pat. Appl.  1981,  EP 44:  214 
    Google Scholar
  • 7a Harusawa S. Yoneda R. Kurihara T. Hamada Y. Shioiri T. Chem. Pharm. Bull.  1983,  31:  2932 
    CrossrefGoogle Scholar
  • 7b Review: Kurihara T. Harusawa S. Yoneda R. J. Synth. Org. Chem. Jpn.  1988,  46:  1164 
    CrossrefGoogle Scholar
  • 7c For a review of 4 as a coupling reagent: Shioiri T. J. Synth. Org. Chem. Jpn.  1979,  37:  856 
    CrossrefGoogle Scholar
  • 7d For other methods to synthesize cyanohydrin O-phosphates, see: Micó I. Nájera C. Tetrahedron  1993,  49:  4327 ; and references therein
    CrossrefGoogle Scholar
  • 8 Baeza A. Casas J. Nájera C. Sansano JM. Saá JM. Angew. Chem. Int. Ed.  2003,  42:  3143 
    CrossrefPubMedGoogle Scholar
  • 9 Guzmán A. Díaz E. Synth. Commun.  1997,  27:  3035 ; and references therein
    Google Scholar
  • 10 The phosphine oxides 3 were synthesized form corresponding phosphines: Kim RD. Stevens CH. Polyhedron  1994,  13:  727 
    CrossrefGoogle Scholar
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General Procedure for the Cyano-Phosphorylation Reaction. To 3a (164.6 mg, 0.3 mmol) in a test tube were added the (S)-YLB·H2O solution (5.00 mL, 0.3 mmol, 0.06 M, THF) [2] and BuLi (0.3 mmol) in hexane at r.t. After dissolving 3a completely, the mixture was cooled to -78 °C, and 5a (3.0 mmol) in THF (4.50 mL) was added to the catalyst mixture. After stirring for 10 min at -78 °C, 4 (0.55 mL, 3.6 mmol) in THF (0.50 mL) was slowly added to the reaction mixture over 1 h, and the reaction mixture was stirred at -78 °C for additional 1 h. Then, HOAc in THF cooled to -78 °C was added to the solution, and the mixture was diluted with H2O. The organic component was extracted with EtOAc. The organic layer was washed with sat. aq NaHCO3, H2O, brine, and dried over Na2SO4. After evaporating solvent, the residue was purified by silica gel flash column chromatography (hexane-EtOAc = 7:1) to give 6a (97% yield, 92% ee, R); colorless oil. IR (neat): ν = 1269, 1024 cm-1. 1H NMR (CDCl3): δ = 1.16 (dt, J ( H,P) = 0.6 Hz, J = 7.0 Hz, 3 H), 1.32 (dt, J ( H,P) = 0.6 Hz, J = 7.0 Hz, 3 H), 3.92-3.99 (m, 2 H), 4.12-4.17 (m, 2 H), 6.02 (d, J ( H,P) = 8.6 Hz, 1 H), 7.39-7.40 (m, 3 H), 7.49-7.50 (m, 2 H). 13C NMR (CDCl3): δ = 15.8 (d, J ( C,P) = 7.3 Hz), 16.0 (d, J ( C,P) = 7.1 Hz), 64.6 (d, J ( C,P) = 6.3 Hz), 64.8 (d, J ( C,P) = 6.1 Hz), 66.5 (d, J ( C,P) = 4.1 Hz), 116.1 (d, J ( C,P) = 6.3 Hz), 127.5, 129.2, 130.6, 132.4 (d, J ( C,P) = 4.1 Hz). 31P NMR (CDCl3): δ =
-1.93. LRMS (ESI, MeOH): m/z = 292 [M + Na+]. HRMS (FAB): m/z [N + H+] calcd for C12H17NO4P: 270.0890; found: 270.0894. [α]D 21.7 +18.9 (c 1.2, CHCl3; 92% ee, R); HPLC (DAICEL CHIRALPAK®) AD-H, hexane-2-PrOH = 9:1, flow rate = 1.0 mL/min, retention time 14.5 min (S)/17.1 min (R). The absolute configuration of 6a was determined comparing retention time in HPLC analysis with that of the authentic product synthesized from commercially available (R)-mandelonitrile (Aldrich Co. Ltd.) with 4.

12

Detailed mechanistic studies of asymmetric cyanation reaction using YLB(1) and the cyanide source 2 and 4 will be reported elsewhere in due course.