First utilization of a homochiral ruthenium porphyrin as enantioselective epoxidation catalyst

Tetrahedron Letters

Volumn 37, Issue 40, 1996, Pages 7325-7328

  Gross, Zeev ^a   Ini, Santiago ^a   Kapon, Moshe ^a   Cohen, Shmuel ^b  

^a TECHNION ISRAEL INSTITUTE OF TECHNOLOGY   (Israel)

^b HEBREW UNIVERSITY OF JERUSALEM   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

EPOXIDE;

ARTICLE; CATALYSIS; CHIRALITY; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0030607241     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)01599-7     Document Type: Article

References (18)

1. 1. Meunier, B. Metalloporphyrins Catalyzed Oxidations; Montanari, F., Casella, L. Eds.; Kluwer Academic Publishers: Dordrecht, 1994; chapter 1. Mansuy, D. Coord. Chem. Rev. 1993, 125, 129-141.
2. 1. Meunier, B. Metalloporphyrins Catalyzed Oxidations; Montanari, F., Casella, L. Eds.; Kluwer Academic Publishers: Dordrecht, 1994; chapter 1. Mansuy, D. Coord. Chem. Rev. 1993, 125, 129-141.
3. 2. Groves, J. T.; Quinn, R. J. Am. Chem. Soc. 1985, 107, 5790-5792. Tavares, M.; Ramasseul, R.; Marchon, J.-C; Bachet, B.; Brassy, C.; Mornon, J.-P. J. Chem. Soc., Perkin Trans. 2 1992, 1321-9.
4. 2. Groves, J. T.; Quinn, R. J. Am. Chem. Soc. 1985, 107, 5790-5792. Tavares, M.; Ramasseul, R.; Marchon, J.-C; Bachet, B.; Brassy, C.; Mornon, J.-P. J. Chem. Soc., Perkin Trans. 2 1992, 1321-9.
5. 3. Groves, J. T.; Myers, R. S. J. Am. Chem. Soc. 1983, 105, 5791-5796.
6. 4. Collman, J. P.; Zhang, X.; Lee, V. J.; Uffelman, E.; Brauman, J. I. Science 1993, 261, 1404-1411.
7. 5. (a) Le Maux, P.; Bahri, H.; Simoneaux, G. Inorg. Chem. 1995, 34, 4691-4697, and references therein.
8. (b) Mazzanti, M.; Marchon, J. C.; Tirowska-Tyrk, I.; Scheldt, W. R. J. Inorg. Biochem. 1995, 59, 504.
9. (c) For stoichiometric epoxidation by a chiral non-porphyrinic ruthenium complex, see: Fung, W.-H.; Cheng, W.-C.; Yu, W.-Y.; Che, C-M.; Mak, T. C. W. J. Chem. Soc., Chem. Commun. 1995, 2007-8.
10. 6. Ini, S.; Kapon, M.; Cohen, S.; Gross, Z. Tetrahedron: Asymm. 1996, 7, 659-662.
11. 7. Collman, J. P.; Lee, V. J.; Kellen-Yuen, C. J.; Zhang, X.; Ibers, J. A.; Brauman, J. I. J. Am. Chem. Soc. 1995, 117, 692-703.
12. 8. Naruta, Y.; Ishihara, N.; Tani, F.; Maruyama, K. Bull. Chem. Soc. Jpn. 1993, 66, 158-166.
13. 9. Palucki, M.; Pospisil, P. J.; Zhang, W.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 9333-4.
14. -1, LP and absorption corrections were performed, scan mode ω/2θ. Reflections collected 4109, independent reflections 3683. The Ru and part of the light atoms were found by direct methods using SHELXS86 (Sheldrick, G. M. Acta Cryst. 1990, A46, 467). The remaining non hydrogen atoms were located by Fourier difference maps and refined against F2 using SHELXL93 (Sheldrick, G. M., SHELXL93 program for the refinement of crystal structures, University of Gottingen, Germany). The Ru and bridged porphyrin were refined anisotropically, hydrogens placed at calculated positions, whereas disordered CO, water and ethanol molecules were refined isotropically. The water and CO ligands were found statistically disordered around the Ru atom. Total number of parameters was 454, R=0.052 and wR=0.158 for 3198 Fo >4 σ (Fo). The Ru-bridged porphyrin is located on a crystallographic twofold axis. Crystallographic data for the structure reported in this paper have been submitted as supplementary material for deposition with the Cambridge Crystallographic Data Centre.
15. 11. Reactions with iodosylbenzene were performed for 1h at 25 °C with 1 μmol catalyst, 100 μmol oxidant, and 1 mmol styrene in 2 mL of solvent. Reactions with 2,6-dichloropyridine N-oxide were performed for 3 h at 25 °C with 1 μmol catalyst, 330 μmol oxidant, and 330 μmol of styrene in 2 mL of Benzene under Ar. At the end of the reactions, the solvent, olefin, epoxide, and iodobenzene were separated from the reaction mixture by bulb to bulb vacuum transfer, leaving behind the catalyst, unreacted oxidant, and 2,6-dichloropyridine. The chemical yields and the enantiomeric excesses were determined by GC, utilizing a Cyclodex -B chiral capillary column. The absolute configuration of the major isomer in all cases was found to be R(+)-styrene oxide, by comparison to an Aldrich product. In the reactions with iodosylbenzene the reported yields are relative to the other product, iodobenzene. In the reactions with 2,6-dichloropyridine N-oxide, the conversion percentages are relative to styrene, determined by addition of a calculated amount of iodobenzene to the purified reaction mixtures.
16. 3): δ 8.65 (d, J = 4.77 Hz, 4H), 8.55 (d, J = 5.01 Hz, 4H), 7.73 (t, J = 8.52 Hz, 4H), 7.22-7.38 (meta-H covered by solvent peak), 4.89 (d, J = 10.08 Hz, 4H), 4.61 (d, J= 8.71 Hz, 4H), 4.43 (t, J = 8.88 Hz, 4H), 4.22 (d, J = 10.63 Hz, 4H), 3.75 (d, J = 8.86 Hz, 4H), 2.58 (t, J = 8.46 Hz, 4H), 0.77 (s, 12H), -0.78 (s, 12H).
17. 13. Othake, H.; Higuchi, T.; Hirobe, M. Heterocycles 1995, 40, 867-903.
18. 14. Groves, J. T.; Quinn, R. Inorg. Chem. 1984, 23, 3844-6.