PDF herunterladen
Synlett 2009(4): 667-670  
DOI: 10.1055/s-0028-1087811
CLUSTER
© Georg Thieme Verlag Stuttgart ˙ New York

Guanidine-Urea Bifunctional Organocatalyst for Asymmetric Epoxidation of 1,3-Diarylenones with Hydrogen Peroxide

Shinji Tanaka, Kazuo Nagasawa*
Department of Biotechnology and Life Science, Faculty of Technology, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan
Fax: +81(42)3887295; e-Mail: knaga@cc.tuat.ac.jp;
Weitere Informationen

Publikationsverlauf

Received 22 September 2008
Publikationsdatum:
16. Februar 2009 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

A highly enantioselective catalytic epoxidation reaction to the electron-deficient α,β-unsaturated olefin moieties of diaryl­enones was achieved with high chemical yield by using aqueous hydrogen peroxide in the presence of a newly developed guanidine-urea bifunctional organocatalyst. These functional groups were suggested to perform cooperatively by interacting with guanidine-­hydrogen peroxide and urea-enones, respectively.

Key words

guanidine - urea - hydrogen peroxide - epoxidation - electron-deficient olefin

    References and Notes

  • 1a Noyori R. Asymmetric Catalysis in Organic Synthesis   John Wiley and Sons; New York: 1994. 
    Google Scholar
  • 1b Comprehensive Asymmetric Catalysis   Jacobsen EN. Pfaltz A. Yamamoto H. Springer; New York: 1999. 
    Google Scholar
  • 1c Catalytic Asymmetric Synthesis   2nd ed.:  Ojima I. Wiley; New York: 2000. 
    Google Scholar
  • 1d Lauret C. Tetrahedron: Asymmetry  2001,  12:  2359 
    Google Scholar
  • For reviews, see:
  • 2a Porter MJ. Skidmore J. Chem. Commun.  2000,  1215 
    Google Scholar
  • 2b Nemoto T. Ohoshima T. Shibasaki M. J. Synth. Org. Chem. Jpn.  2002,  60:  94 
    Google Scholar
  • 2c Lauret C. Roberts SM. Aldrichimica Acta  2002,  35:  47 
    Google Scholar
  • 3a Noyori R. Aoki M. Sato K. Chem. Commun.  2003,  1977 
    Google Scholar
  • 3b Campos-Martin JM. Blanco-Brieva G. Fierro JLG. Angew. Chem. Int. Ed.  2006,  45:  6962 ; and references cited therein
    Google Scholar
  • 4a Juliá S. Masana J. Vega JC. Angew. Chem., Int. Ed. Engl.  1980,  19:  929 
    Google Scholar
  • 4b Juliá S. Guixer J. Masana J. Rocas J. Colonna S. Annuziata R. Molinari H. J. Chem. Soc., Perkin Trans. 1  1982,  1317 
    Google Scholar
  • 5a Arai S. Tsuge H. Shioiri T. Tetrahedron Lett.  1998,  39:  7563 
    Google Scholar
  • 5b Arai S. Tsuge H. Oku M. Miura M. Shioiri T. Tetrahedron  2002,  58:  1623 
    Google Scholar
  • 5c Dehmlow EV. Düttmann S. Neumann B. Stammler H.-G. Eur. J. Org. Chem.  2002,  2087 
    Google Scholar
  • 5d Berkessel A. Gasch N. Glaubiz K. Koch C. Org. Lett.  2001,  3:  3839 
    Google Scholar
  • 5e Kelly DR. Roberts SM. Biopolymers  2006,  84:  74 
    Google Scholar
  • 5f Berkessel A. Koch B. Toniolo C. Rainaldi M. Broxterman QB. Kaptein B. Biopolymers  2006,  84:  90 
    Google Scholar
  • 5g Geller T. Gerlach A. Krüger CM. Militzer H.-C. Tetrahedron Lett.  2004,  45:  5065 
    Google Scholar
  • 5h Geller T. Krüger CM. Militzer H.-C. Tetrahedron Lett.  2004,  45:  5069 
    Google Scholar
  • 5i Yi H. Zou G. Li Q. Chen Q. Tang J. He M.-y. Tetrahedron Lett.  2005,  46:  5665 
    Google Scholar
  • 5j Hori K. Tamura M. Tani K. Nishiwaki N. Ariga M. Tohda Y. Tetrahedron Lett.  2006,  47:  3115 
    Google Scholar
  • 5k Sundén H. Ibrahem I. Córdova A. Tetrahedron Lett.  2006,  47:  99 
    Google Scholar
  • 5l Zhao G.-L. Ibrahem I. Sundén H. Córdova A. Adv. Synth. Catal.  2006,  349:  1210 
    Google Scholar
  • 6 Marigo M. Franzén J. Poulsen TB. Zhuang W. Jørgensen KA. J. Am. Chem. Soc.  2005,  127:  6964 
    CrossrefPubMedGoogle Scholar
  • 7 Jew S.-s. Lee JH. Jeong B.-S. Yoo M.-S. Kim M.-J. Lee J. Choi S.-h. Lee K. Lah MS. Park H.-g. Angew. Chem. Int. Ed.  2005,  44:  1383 
    CrossrefPubMedGoogle Scholar
  • 8 Wang X. Reisinger CM. List B. J. Am. Chem. Soc.  2008,  130:  6070 
    CrossrefPubMedGoogle Scholar
  • 9a Ishikawa T. Isobe T. Chem. Eur. J.  2002,  8:  552 
    Google Scholar
  • 9b McManus JC. Carey JS. Taylor RJK. Synlett  2003,  365 
    Google Scholar
  • 9c McManus JC. Genski T. Carey JS. Taylor RJK. Synlett  2003,  369: 
    Google Scholar
  • 9d Allingham MT. Howard-Jones A. Murphy PJ. Thomas DA. Caulkett PWR. Tetrahedron Lett.  2003,  44:  8677 
    Google Scholar
  • 9e Kumamoto T. Ebine K. Endo M. Araki Y. Fushimi Y. Miyamoto I. Ishikawa T. Isobe T. Fukuda K. Heterocycles  2005,  66:  347 
    Google Scholar
  • 9f Ishikawa T. Kumamoto T. Synthesis  2006,  737 
    Google Scholar
  • 9g Kita T. Shin B. Hashimoto Y. Nagasawa K. Heterocycles  2007,  73:  241 
    Google Scholar
  • 9h Shin B. Tanaka S. Kita T. Hashimoto Y. Nagasawa K. Heterocycles  2008,  76:  801 
    Google Scholar
  • 9i Terada M. Nakano M. Heterocycles  2008,  1049 
    Google Scholar
  • 10a Sohtome Y. Hashimoto Y. Nagasawa K. Adv. Synth. Catal.  2005,  347:  1643 
    Google Scholar
  • 10b Sohtome Y. Takemura N. Iguchi T. Hashimoto Y. Nagasawa K. Synlett  2006,  144 
    Google Scholar
  • 10c Sohtome Y. Hashimoto Y. Nagasawa K. Eur. J. Org. Chem.  2006,  2894 
    Google Scholar
  • 10d Sohtome Y. Takemura N. Takada K. Takagi R. Iguchi T. Nagasawa K. Chem. Asian J.  2007,  2:  1150 
    Google Scholar
  • 10e Takada K. Takemura N. Cho K. Sohtome Y. Nagasawa K. Tetrahedron Lett.  2008,  49:  1623 
    Google Scholar
  • 11a Sohtome Y. Tanatani A. Hashimoto Y. Nagasawa K. Chem. Pharm. Bull.  2004,  52:  477 
    Google Scholar
  • 11b Sohtome Y. Tanatani A. Hashimoto Y. Nagasawa K. Tetrahedron Lett.  2004,  45:  5589 
    Google Scholar
  • 11c Maher DJ. Connon SJ. Tetrahedron Lett.  2004,  45:  1301 
    Google Scholar
  • 12 Howard-Jones A. Murphy PJ. Thomas DA. J. Org. Chem.  1999,  64:  1039 
    CrossrefGoogle Scholar
  • 13a Lu C.-S. Hughes EW. Giguère PA. J. Am. Chem. Soc.  1941,  63:  1507 
    Google Scholar
  • 13b Aida K. J. Inorg. Nucl. Chem.  1963,  25:  165 
    Google Scholar
  • 13c Cooper M. Heaney H. Newbold AJ. Sanderson WR. Synlett  1990,  533 
    Google Scholar
  • 13d Heaney H. Aldrichimica Acta  1993,  26:  35 
    Google Scholar
  • 15a Schreiner PR. Wittkopp A. Org. Lett.  2002,  4:  217 
    Google Scholar
  • 15b Wittkopp A. Schreiner PR. Chem. Eur. J.  2003,  9:  407 
    Google Scholar
  • 17a Lattanzi A. Org. Lett.  2005,  7:  2579 
    Google Scholar
  • 17b Li Y. Liu X. Yang Y. Zhao G. J. Org. Chem.  2007,  72:  288 
    Google Scholar
  • 17c Ye J. Wang Y. Chen J. Liang X. Adv. Synth. Catal.  2004,  346:  691 
    Google Scholar
  • 17d Kumaraswamy G. Sastry MNV. Jena N. Kumarb KR. Vairamanic M. Tetrahedron: Asymmetry  2003,  14:  3797 
    Google Scholar
  • 17e Ooi T. Ohara D. Tamura M. Maruoka K. J. Am. Chem. Soc.  2004,  126:  6844 
    Google Scholar
  • 21 Sohtome Y. Takemura N. Takagi R. Hashimoto Y. Nagasawa K. Tetrahedron  2008,  64:  9423 ; and references cited therein
    CrossrefGoogle Scholar
14

Synthesis of Catalyst 1a and Spectral Data for 1a-e
To a solution of guanidine (S,S)-1f ¹0a (258 mg, 0.317 mmol) in CH2Cl2 (3.0 mL) was added TFA (3.0 mL) at 0 ˚C. The reaction mixture was warmed to r.t. and stirred for 2 h. The resulting mixture was concentrated in vacuo to give diamine. To a solution of the diamine in THF (6.0 mL) was added phenyl isocyanate (0.21 mL, 1.90 mmol), and the mixture was stirred for 12 h. The resulting mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel (n-hexane-EtOAc = 4:1 to 1:1, CHCl3-MeOH = 9:1) to give 1a as a TFA salt (Scheme  [¹] ). The counteranion of 1a was exchanged into Cl- by treatment with sat. aq NH4Cl and EtOAc solution, and gave 1a as a HCl form in 81% yield from 1f (219 mg, 0.257 mmol).
Compound 1a: [α]D ²4 -41.2 (c 1.3, CHCl3). ¹H NMR (400 MHz, CD3OD): δ = 7.33-7.10 (m, 18 H), 6.93 (t, J = 7.4 Hz, 2 H), 4.11 (br s, 2 H), 3.45-3.32 (m, 4 H), 3.16 (t, J = 7.3 Hz, 2 H), 3.03 (dd, J = 4.5, 14.1 Hz, 2 H), 2.79 (dd, J = 9.6, 13.7 Hz, 2 H), 1.59 (m, 2 H), 1.34-1.14 (m, 30 H), 0.88 (t, J = 7.3 Hz, 3 H). ¹³C NMR (100 MHz, CD3OD): δ = 158.51, 156.33, 140.52, 138.97, 130.22, 129.83, 129.68, 127.78, 123.67, 120.18, 52.46 (br), 47.63 (br), 43.12, 39.32, 33.09, 30.78 (br), 30.69, 30.66, 30.49, 30.39, 29.75, 27.99, 23.75, 14.48. ESI-HRMS: m/z calcd for C51H74N7O2 [M + H+]: 816.5904; found: 816.5895.
Compound 1b: [α]D ²5 -11.3 (c 1.1, CHCl3). ¹H NMR (400 MHz, CD3OD): δ = 7.94 (s, 4 H), 7.44 (s, 2 H), 7.31-7.14 (m, 10 H), 4.14 (br s, 2 H), 3.41 (d, J = 5.0 Hz, 4 H), 3.18 (t, J = 7.3 Hz, 2 H), 3.07 (dd, J = 4.0, 13.9 Hz, 2 H), 2.80 (dd, J = 9.5, 13.9 Hz, 2 H), 1.61 (m, 2 H), 1.34-1.08 (m, 30 H), 0.88 (t, J = 6.9 Hz, 3 H). ¹³C NMR (100 MHz, CD3OD): δ = 157.82, 156.31, 142.99, 138.79, 133.13 (q, J CF = 32.6 Hz), 130.14, 129.66, 127.81, 124.76 (d, J CF = 271.3 Hz), 120.70, 118.98, 115.79, 52.66 (br) 47.46, 43.10, 39.20, 33.08, 30.75 (br), 30.61, 30.54, 30.47, 30.16, 29.64, 27.92, 23.74, 14.46. ESI-HRMS: m/z calcd for C55H70F12N7O2 [M + H+]: 1088.5399; found: 1088.5370.
Compound 1c: [α]D ²6 -24.5 (c 1.4, CHCl3). ¹H NMR (400 MHz, CD3OD): δ = 7.32-7.17 (m, 10 H), 6.97 (d, J = 9.6 Hz, 4 H), 6.46 (t, J = 9.2 Hz, 2 H), 4.10 (br s, 2 H), 3.39 (d, J = 5.5 Hz, 4 H), 3.18 (t, J = 7.3 Hz, 2 H), 3.07 (dd, J = 4.6, 13.8 Hz, 2 H), 2.79 (dd, J = 9.6, 14.2 Hz, 2 H), 1.63 (m, 2 H), 1.35-1.07 (m, 30 H), 0.88 (t, J = 6.4 Hz, 3 H). ¹³C NMR (100 MHz, CD3OD): δ = 164.61 (dd, J CF = 15.3, 243.4 Hz), 157.77, 156.22, 143.55 (t, J CF = 13.5 Hz), 138.81, 130.18, 129.64, 127.77, 102.09 (dd, J CF = 8.6, 21.1 Hz), 52.54 (br), 47.49 (br), 43.16, 39.22, 33.07, 30.78 (br), 30.71, 30.65, 30.48, 30.38, 29.76, 28.03, 23.74, 14.50. ESI-HRMS: m/z calcd for C51H70F4N7O2 [M + H+]: 888.5527; found: 888.5572.
Compound 1d: [α]D ²5 -40.4 (c 1.1, CHCl3). ¹H NMR (400 MHz, CD3OD): δ = 8.04 (s, 4 H), 7.47 (s, 2 H), 3.78 (br s, 2 H), 3.42 (dd, J = 13.8, 5.1 Hz, 2 H), 3.25 (m, 2 H), 3.17 (t, J = 7.4 Hz, 2 H), 1.94 (br, 2 H), 1.58 (m, 2 H), 1.33-1.08 (m, 30 H), 1.03 (d, J = 6.4 Hz, 6 H), 1.01 (d, J = 6.4 Hz, 6 H), 0.88 (t, J = 6.9 Hz, 3 H). ¹³C NMR (100 MHz, CD3OD): δ = 158.30, 156.31, 143.15, 133.20 (q, J CF = 32.6 Hz), 128.84, 124.78 (d, J CF = 272.2 Hz), 120.73, 118.84, 115.68, 55.92 (br), 46.04, 43.03, 33.08, 31.04 (br), 30.75 (br), 30.70, 30.62, 30.52, 30.48, 30.19, 29.80, 27.87, 23.74, 20.19, 17.62 14.46. ESI-HRMS: m/z calcd for C47H70F12N7O2 [M + H+]: 992.5399; found: 992.5373.
Compound 1e: [α]D ²6 -8.9 (c 1.1, CHCl3). ¹H NMR (400 MHz, CD3OD): δ = 8.04 (s, 4 H), 7.46 (s, 2 H), 3.91 (br s, 2 H), 3.41-3.14 (m, 6 H), 1.64 (m, 2 H), 1.29 (d, J = 6.9 Hz, 6 H), 1.27-1.10 (m, 30 H), 0.87 (t, J = 6.9 Hz, 3 H). ¹³C NMR (100 MHz, CD3OD): δ = 157.80, 156.25, 143.11, 133.15 (q, J CF = 32.6 Hz), 128.84, 124.79 (d, J CF = 272.2 Hz), 120.73, 119.00, 115.72, 47.05 (br), 43.13, 33.08, 30.75 (br), 30.70, 30.61, 30.52, 30.48, 30.14, 29.63, 27.90, 23.74, 18.34, 14.46. ESI-HRMS: m/z calcd for C43H62F12N7O2 [M + H+]: 936.4773; found: 936.4734.

Scheme 1

16

We recycled the catalyst 1b five times under the conditions of entry 11 in Table  [¹] . In these reactions, the yields and enantioselectivities were as follows: 2nd run: 95% with 90% ee; 3rd run: 99% with 90% ee; 4th run: 99% with 91% ee; and 5th run: 99% with 89% ee.

18

Typical Procedure for Asymmetric Epoxidation of 4a
A mixture of enone 4a (20.8 mg, 0.10 mmol) and guanidine-urea organocatalyst (S,S)-1b (5.6 mg, 0.005 mmol, 5 mol%) in toluene (0.95 mL) was cooled at -10 ˚C. To the mixture was added 1 M aq NaOH (0.050 mL, 0.050 mmol) and 30% aq H2O2 (0.051 mL, 0.50 mmol of H2O2). The mixture was stirred vigorously at -10 ˚C under argon atmosphere for 6 h. To the reaction mixture was added sat. aq NH4Cl, and the organic layer was extracted with EtOAc. The combined organic extracts were dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (n-hexane-EtOAc = 100:1 to 10:1) to give epoxy ketone 5a (22.3 mg, 99%) and catalyst 1b was quantitatively recovered (5.6 mg, >99%). The ee and absolute configuration of the epoxy ketone 5a was determined by HPLC using a chiral column.
Spectral Data and HPLC Data for Epoxy Ketone 5a
[α]D ²4 -210.1 (c 0.83, CHCl3). ¹H NMR (400 MHz, CDCl3): δ = 8.02 (d, J = 6.9 Hz, 2 H), 7.63 (t, J = 7.8 Hz, 1 H), 7.49 (t, J = 7.8 Hz, 2 H), 7.45-7.35 (m, 5 H), 4.31 (d, J = 1.8 Hz, 1 H), 4.08 (d, J = 1.8 Hz, 1 H). HPLC separation conditions: Chiralcel OD-H, 0.46 cm (ϕ) × 25 cm (L), hexane-2-PrOH = 98:2, 1.00 mL/min, t R(minor) = 19.5 min (2S,3R); t R(major) = 20.4 min (2R,3S).¹7a

19

In the case of aliphatic substituted enones, enantioselec-tivities were moderate to low (ex. R¹ = Me, R² = Ph, 99% yield with 41% ee).

20

NMR studies were performed in C6D6.