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Journal of Molecular Catalysis A: Chemical 160 Ž2000. 217–227 www.elsevier.

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Chiral Ni žII/ Schiff base complex-catalysed enantioselective epoxidation of prochiral non-functionalised alkenes
R.I. Kureshy ) , N.H. Khan, S.H.R. Abdi, S.T. Patel, P. Iyer, E. Suresh, P. Dastidar
Silicates and Catalysis Discipline, Central Salt and Marine Chemicals Research Institute, Gijubhai Badheka Marg., BhaÕnagar-364 002, India Received 3 January 2000; accepted 15 March 2000

Abstract The synthesis, characterisation and single crystal X-ray structures of square planar NiŽII. chiral Schiff base complexes with N2 O 2-type ligands have been described. These catalysts were used for enantioselective epoxidation of non-functionalised alkenes viz. 1-hexene, 1-octene, styrene, 4-chloro-, 4-nitrostyrene and 1,2-dihydronaphthalene using NaOCl as oxidant, giving excellent conversions with long chain alkenes while ee ’s were moderate to good. A mechanism for the NiŽII.-catalysed epoxidation with NaOCl is proposed. q 2000 Elsevier Science B.V. All rights reserved.
Keywords: Alkenes; Asymmetric induction; Epoxidation; Imines; Non-functionalised

1. Introduction The design of catalysts that ensures high enantioselectivity in the epoxidation of nonfunctionalised alkenes constitutes one of the most significant challenges in asymmetric synthesis w1–3x. In principle, it may be attainable with systems that can exert high asymmetric induction without requiring any specific functionality on the substrate for catalyst precoordination w4,5x. The major advances in this field have been achieved with chiral porphyrins w6,7x and Jacobsen et al. w5,8x with the system of Katsuki et al. w9, 10x based on chiral MnŽ III.
) Corresponding author. Tel.: q 91-2-7856-7760; fax: q 91-27856-6970. E-mail addresses: salt@bhavnagar.com, salt@csir.res.in ŽR.I. Kureshy..

Schiff base complexes using NaOCl as oxidant. Several other oxidants, such as iodosyl benzene w10x, molecular oxygen w11x, H 2 O 2 w12x, Bu 4 NIO4 w13x, dimethyldioxirane w14x and m-chloroperbenzoicacid w15x with related complexes, were also explored. Mononuclear, as well as dinuclear metal centers, are commonly found in the active site of various oxygenase w16–18x and the information on key structural features and factors governing oxygenase activity is rapidly increasing w19,20x. The first example of olefin epoxidation by nickelŽII. catalysts with iodosylbenzene was shown by Koola and Kochi w21x. Later, Burrows et al. w22–24x also reported the synthesis, crystal structure of nickelŽII. complexes and has used them as catalysts in the presence of iodosylbenzene, as well as hypochlorite for epoxidation of a wide variety of olefins. Dinuclear nickelŽII. complexes have

1381-1169r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved. PII: S 1 3 8 1 - 1 1 6 9 Ž 0 0 . 0 0 2 1 3 - 2

1 H NMR ŽCDCl 3 . 4 . Found: C.2-dihydronaphthalene using NaOCl as oxidant. N. 1 H NMR spectroscopy.2cyclohexane diamine and 1 S.14 Žs. N X-bis Ž4-hydroxy-6-methyl-2-pyrone. 2. 2H.2-diphenyl ethylene diamine a Ž0. 70. Synthesis of chiral Schiff bases The chiral Schiff bases 1 S. styrene. d. and 1X S-Ž q. -1.46. 6H. CoŽ II.2 R-Ž y. N.50.3.2X-diamino diphenyl ethylene diamine (DHPS). we are reporting here the synthesis. CH 3 .85 Žs. H 5 .2X-cyclohexane diamine Ž CyLS. H 9 . -1. 1. OH ketorenol. N X-bis Ž 4-hydroxy-6-methyl-2-pyrone . 3-acetyl-4-hydroxy6-methyl-2-pyrone Ž National. Yield 70%.. H 7 . 2H. Calcd.58.57 Žs. m. H 7 . the solvent was concentrated on rotaevaporator and the desired ligand were precipitated by 40–60 petroleum ether.27. 7.2X-diphenyl diaminoethane. s 1625 cmy1. 3-acetylidine4 1X . 1S.2 S-Žq.. 4-chlorostyrene. .65 Žs. We have been involved in the evaluation of the epoxidation capacity of prochiral nonfunctionalised alkenes using RuŽ III.39 Žm. Preparation of Ni(II) chiral Schiff base complexes Appropriate amount of the chiral Schiff bases Ž0.: d . IRŽKBr. 2H. 5. CH 3 .75. 2. IR-. 6. 6.2 S-Žq. .2 S-Ž q . H. 70.1.-CyLS were characterised by microanalysis. H 9 . dichloromethane and acetonitrile were dried and distilled by commonly used procedures.. CH 3 . : d . N X-bis Ž 4-hydroxy-6methyl-2-pyrone.29–7..-N.2.p. s 1625 cmy1. IRŽKBr. r Journal of Molecular Catalysis A: Chemical 160 (2000) 217–227 also been synthesised and used for epoxidation reactions by Gelling et al. H. 5.2 R-Ž y . -DPHS and 1 R . 2.01 mol.I. 1hexene and 1.79 Žbs. After the completion of reaction. Yield 65%.7. 1.48. for C 30 H 28 N2 O6 : C. for C 22 H 26 N2 O6 : C. RuŽ II. S-Ž q.12 Žs.-1. 5.. -N. 1-octene. 1-hexene.2 S-Ž q. dissolved in ethanol was allowed to reflux in inert atmosphere with NiŽCH 3 COO. 1 S.001 mol. Schiff base complexes with a view to use them as active catalysts for enantioselective epoxidation of representative non-functionalised alkenes viz.N X-bis{(4-hydroxy-6-methyl2-pyrone)3-acetylidine} 1X . Found: C.N X-bis{(4-hydroxy-6-methyl-2pyrone)3-acetylidine} 1X . 8H. phenyl.72. styrene. Kureshy et al.1. 5. HX1 and HX2 .. .2X-diaminopropane ŽPROS. 4-chlorostyrene. and the .2 R-Žy. 1 R . -diphenyldiaminoethane.45.. 3-acetylidine4 1X . 1 S. aromatic phenyl. 6H. HX3 to HX6 . -1.. 3-acetylidine 4 1X . resulting solution was refluxed for 7 9 h Ž TLC checked. were synthesised and characterized according to our previous communication w30x.2 R-Ž y .2-dihydronaphthalene ŽAldrich.2R-(y )-N. OH ketorenol. As part of this pursuit.-CyLS were synthesised by the following method.2 S-Žq. was added to the hot methanolic solution of 3-acetyl 4-hydroxy 6-methyl 2-pyrone Ž 0. 63. 2 2. 2H. Calcd. 3. 4-nitrostyrene. 2208C. .2 R-Žy. N. H. 2.4–1.p.. .2-diaminopropane was resolved from its dl form by the reported procedure w31x. 6H.2cyclohexane diamine.30. 1-octene and 1. 2. 1R. 5. 2. and NiŽII. MnŽIII. characterization and X-ray single crystal determination of mononuclear chiral NiŽ II. 2058C. were either used as such or passed through a short column of alumina neutral if it contains stabilizer.68 Žs.-cyclohexane diamine.02 mol. -diphenyldiaminoethane. The chiral Schiff bases 1 S. Ž DPHS. 1 R . 63. 2H. 6. m.2S-(q)-N. and 15. 4-nitrostyrene. chiral Schiff base complexes w26–30x.2 S-Ž q. : n ŽC5N.53 Žm. H. 5H.. 1 H NMR ŽCDCl 3 . 5. -N .26 Žbs. ethanol. . N..2 R-Žy. while 1 S. w25x. 6H.2X-cyclohexane diamine (CyLS). 2. Experimental Nickel acetate ŽSisco. 1 R .218 R.: n Ž C5N. Methanolic solution of 1 R . -DPHS and 1 R . ŽCH 2 . CH 3 . and 14. 6.8 Žm. Solvents methanol.

each molecules in the asymmetric units was refined in blocks using the program SHELX-97 w34x in all the three complexes.73.37.. r Journal of Molecular Catalysis A: Chemical 160 (2000) 217–227 219 Ž0.. 6H. 5 mho cmy1 moly 1 : D Epa s q0..R. Three standard reflections were monitored after every 100 reflections during the entire period of data collection. N.28 Žs. 7. refinement of the cell parameters and intensity measurements were carried out using the program CAD-4 PC w32x. 234 Ž5422.-DPHS NiŽII. 5. 2H. 3... IRŽKBr. were used for getting the accurate cell dimensions. ŽMeOH. aromatic Phenyl.7 Configuration Ž S . cmy1 1585 n ŽH– C5N. H 7 .-DPHS NiŽII.56 Žm. : 238 Ž5598. in the range u s 2– MoK a radiation Ž0.83 Ž m. 5. H 5 . The Lorentz polarization corrections and data reduction were carried out using NRCVAX program w33x. 5 mho cmy1 moly 1 . 2H. Configuration Ž R . . 5. lmax Ž ´ .85 Žs. 2.60 Žs. . 510 Žy1. H 9 .2 R-Ž y.. H 7 . 4..59. 2H.. for C 22 H 24 N2 O6 Ni : C.15: H. 300 Ž6158.. . indicating the stability of the crystal. ŽCH 2 . 1. 2H. 6H. 4. H.001 mol. The overall yield for all the complexes were in the range of 65–70%. H 9 . HX3 to HX6 . .93.2 R-Žy. 63. 1 S.1. w a x tD s q28. ..65–1. N.38. Analytical data for the Ni(II) complex 1R. 346 Žy4.93 Ž s.62 Žs.4.. 332 Ž q 1. Found: C. IR ŽKBr. : d . 4. keeping each molecule in the asymmetric unit and solvent acetonitrile molecule in separate blocks till .2S-(q)-DPHS Ni(II) Calcd. 2.. Crystals of 1 were stable outside the mother liquor. 3. 302 Ž 5369. CH 3 . and 1 S. 56. . 2. ŽMeOH.2R-(y)-CyLs Ni(II) Calcd. 10H. Since the number of observed reflections to parameter ratio was rather low. whereas those of 2 and 3 had to be sealed in Lyndman glass capillary for the X-ray intensity measurements.1..49–7. The analytical data for the Ni(II) complex 1S.78 V. 8H. for 10–13 h.. 2.85 Žbs.PROS NiŽ II. 4 . 1265 n ŽC–O. CH 3 . Found: C. 1 H NMR ŽCDCl 3 . CH 3 . 440 Ž q 2. The solution was filtered and concentrated on rotaevaporator till dryness.. HX1 and HX2 . The structure was solved by direct method for 1 and by Patterson for 2 and 3 using the program SHELX-97 w34x. UV–VIS Ž nm.94.I. CH... . which showed no significant variation. The raw intensity data were corrected for Lorentz polarization effects but not for absorption.7107 A 258 in the case of 1 and 3 and upto u s 22.5.91. H..96.. H 5 .. 314 Ž6293. L M ŽMeOH. L M ŽMeOH..: d .82 V. 264 Ž5868.-CyLS NiŽII. . . . in the presence of triethylamine tetrahydrate Ž0. cmy1 1585 n ŽH–C5N.-PROS NiŽ II. 56.DPHS NiŽII.15 : N.16 : H. The resulting residue was washed in ethanol and dried in vacuum. w a x tD s y28. 1 H NMR ŽCDCl 3 .. The crystal orientation. CD l max Ž D ´ .001 mol. 5. 6H. 2.7. 63.11 Žs. CH 3 . ŽMeOH.16 Žs. UV–VIS Žnm. 365 Ž q 1.58 for 2. CH. All the complexes were tried on to get suitable crystal for X-ray but only complexes S-Ž q. crystallized out in the proper way. 365 Žy3.3. X-ray crystallography Cell parameters and reflection intensities for all the three compounds were measured at room temperature on an Enraf-Nonius CAD-4 X-ray diffractometer using graphite monochromatised ˚ . HX1 and HX2 . 366 Ž5380. CD lmax Ž D ´ . D Epa s q0. Twenty-five high angle reflections Ž u s 9–128. 4. 5. are reported earlier w30x. 505Žq5. The full matrix least squares refinement of all nonhydrogen atoms with isotropic temperature factors was carried out till the convergence reached in all the three cases. . 6H. 2.2 S-Žq. Kureshy et al. 5. Analytical data for the complexes S-Ž q. 1 R . CH. 4.14: N.2 S-Ž q.1. 1260 n ŽC–O. MeOH l max Ž ´ . Progress of the reaction was checked on TLC. and 1 R .61. for C 30 H 26 N2 O6 Ni: C. The full matrix least squares refinement with anisotropic thermal parameters was carried out in blocks.

64 Monoclinic C2 0. 1.185. U ŽA 1847 Ž3. Epoxidation of non-functionalised alkenes by catalysts 1 – 5 Enantioselective epoxidation of styrene.1.185 R1 s Ý < < Fo < y < Fc < <rÝ < Fo <.12 = 0.. After completion of reaction. 2 rÝw Ž Fo2 .328 2632 5552 4054 739 0.0 135. and 1.17 Ž5. respectively. R1 s 0. for 3. 18. 3. r Journal of Molecular Catalysis A: Chemical 160 (2000) 217–227 Table 1 Summary of crystallographic data and parameters for complexes 1. a Ž8.267 Ž9.235. 90. ˚.146 ˚. Molar conductance was measured at room temperature on a Digisun Electronic Conductivity Bridge DI-909. 0.052 Ž wR s 0.42 Ž9. in blocked fashion described earlier.18 = 0.235 Complex 4 C 66 H 61 N7 O12 Ni 2 1261. 1-octene. The final cycles of least-squares refinements. 90. 95. dissolved in 1 ml dichloromethane was stirred with NaOCl at the pH s 11. Žon F . The IR spectra were recorded on Biorad FTS-40 spectrophotometer in KBrrnujol mull. After 1 h.078 Final Ž wR 2. 19. as eluent. 1-octene and 1. for 1. 1hexene. Evaluation of enantiomeric excess was done by GC on chiraldex BDArBPH capillary column.346 2632 4065 2704 739 0. wR 2 s wÝw Ž Fo2 y Fc2 . Schiff base complexes with NaOCl at pH s 11.16 = 0. 4 1.20 = 0.16 Monoclinic P 21 0. 4chlorostyrene. g Ž8. 90. Cyclic . Electronic spectra were recorded on Hewlett-Packard Diode Array spectrophotometer Model 8452A.92 Ž4. After each interval of 1 h.097Ž wR 2 s 0.15. 1 H NMR 200 was recorded on Bruker FX-200 NMR spectrophotometer in CD 3 OD.08 7.06 24. 18. solvent was removed and product was separated by short column of silica gel using hexane : dichloromethane Ž 9:1.748 Ž17.078 Ž wR 2 s 0.14 = 0.891 Ž6. 13.508 Ž7. styrene. 896 Total reflections 3402 1841 Observed reflections w I G 2 s Ž I . The H-atoms were fixed stereochemically using riding model using Shelex-97 or located from the difference Fourier map. 4-nitrostyrene.239 Ž19. yielded the R-value of R1 s 0. Z 2 Dc Žg cmy3 . b ŽA ˚. 90.550 F Ž000. 90. 4.2-dihydronaphthalene Ž1 mmol. 4-chlorostyrene. 0. 4-nitrostyrene.x Parameters refined 514 Final Ž R1.642 Ž15.64 Monoclinic C2 0. Complex 2 C 66 H 61 N7 O12 Ni 2 1261.0 6226 Ž9.20 = 0. Kureshy et al. the reaction mixture was washed with water and dried over sodium sulfate. a ŽA Complex 1 C 38 H 40 N4 O12 Ni 2 862.73 Ž2.097 0.3 as oxidant at room temperature.10 24.0 6311 Ž6. c ŽA 18. 4 1.0 ˚ 3. 2 x1 r 2 convergence is reached.I. 17. Methods Microanalysis of the complexes was done on Perkin-Elmer model 1106.02 mmol.3 was carried out by the following procedure: The chiral catalyst Ž0. 90. 1-hexene. an aliquot was taken from the reaction and analyzed by GLC. Crystallographic data for the compound is summarized in Table 1. Žon F 2 . .220 R.764 Ž5.0 128.0 b Ž8. 2 and 4 Formula M Crystal system Space group Crystal dimensions Žmm.469 Ž9.2-dihydronaphthalene catalysed by chiral NiŽII.052 0. for 2 and R1 s 0.

In the ligand field region. -diphenyldiaminoethane. The IR spectra of the Schiff base ligands showed a broad band near 3380 cmy1 due to n ŽO–H. The intense band near 1585–1590 cmy1 in the complexes is due to coordinated azomethine nitrogen and this band lie at higher wave number in free ligands.2R-Ž y. nm. 5. 2. 1 S . The analytical data of the complexes along with their molar conductance are given in the Experimental section and are consistent with the formation of neutral square planer NiŽII. The electronic spectra of the complexes recorded in methanol show high intensity charge transfer band near 300 Ž ´ s 6158.7..2 R-Ž y . hence. 1. differential pulse voltammogram were recorded with a Princeton Applied Research ŽPAR.. the complex 2 is stereospecifically coordinated to metal such that the gauche chelate ring is exclusively in l form while the complex 4 is totally in d form. substrates and analysis of the product was determined by GLC using Shimadzu GC 14B coupled with PC using 2-m-long. -diphenyldiamino ethane. nm and are assigned to d–d bands Fig. CD spectra of the complexes 2 1S. 5% mesh size 60–80 with FID detector. Japan. 1 R . center Fig.-CyLS Ni(II) were recorded in methanol ŽFig.2-diaminopropane. Schiff base complexes involve the condensation of S-Ž q . The purity of the solvents. instrument using tetrabutyl ammonium perchlorate as supporting electrolyte in dichloromethane.2 S -Ž q . -1. . complexes. Kureshy et al.R. This conformational and configurational behavior is already reported earlier w26–30x.D.2 S-Ž q. This band disappeared on complexation showing the coordination of phenolic oxygen to metal. Synthetic standards of the product were used to determine yields by comparison of peak height and area. The optical rotation of the complexes in methanol was measured by polarimeter Atago. stainless steel column packed with SE 30.2S-(q)DPHS Ni(II) and 4 1R.D. Results and discussion The synthetic strategy for 1–5 neutral square planar chiral NiŽ II. - diaminocyclohexane with 3-acetyl 4-hydroxy 6-methyl 2-pyrone in methanol followed by insertion of NiŽII.2 R-Ž y. 4-mm-O. nm. 3-mm-I. Column temperature programmed between 708C to 1508C and injection temperature 2008C with nitrogen carrier gas flow 30 mlrmin. 1. As both the complexes have opposite absolute configuration. the bands of opposite cotton effect lie near 505 Žq5. The optical yield Ž ee ’s. The CD spectra were recorded in methanol by Jasco Machine Model J-20 Japan. 1 R .. Representative structures of the catalysts. 1 S.I. while the MLCT band lie near 366 Ž ´ s 5380. -diaminocyclohexane. r Journal of Molecular Catalysis A: Chemical 160 (2000) 217–227 221 voltammetry. nm and 510 Žy1. of the product was determined by the integration of peak area of both enantiomers on chiraldex BPH and BDA chiral capillary GC-Column.

I. 2.-. with adopted numbering scheme.36x. The values are consistent with those reported earlier w35. The molecular geometry and conformation of molecules A and B are almost same in all cases. nm. 2 and 4. Structure of complex 2 ŽORTEP. The cyclic voltammetry of the complexes in CH 2 Cl 2 shows reversible oxidation in the range q0. Structure of complex 1 ŽORTEP. ™ ™ 5. ORTEP w37x view of only one molecule with atom numbering scheme is depicted in Figs.5. r Journal of Molecular Catalysis A: Chemical 160 (2000) 217–227 Fig. respectively. However. Fig. with adopted numbering scheme. respectively. SCE using 0. Fig. The absolute configuration is assigned on the basis of known chirality of the diamine used.82 V vs. 3. The ligand p p ) transition lies in higher energy region at 332 Žq1.78 to q0. .1.1 M tetra butyl ammonium perchlorate as supporting electrolyte.. while the d p ) band lies near 365 Žy3. 2 and 4 crystallized with two molecules in an asymmetric unit. CD spectra of Ž — . complex 4 recorded in methanol. with adopted numbering scheme.1. in each case. nm and 440 Žq2. and are spin-forbidden ligand bands. which is designated as molecule A and molecule B. the geometry around NiŽII. 2 and 4 The complexes 1. nm. 5. complex 2 and Ž. Sructure of complex 4 ŽORTEP.1. Kureshy et al.222 R. Structure of complexes 1. Irrespective of the substituents on ethylenediamine collar. center is slightly distorted square planar with metal ion contained well within the coordination plane having maximum Fig. 3–5 for the complexes 1. nm to 346 Žy4. 4.

518. C7. C8. 5. C6. 2 R 2 3 4 5 a Reaction conditions : Substrate Ž1 mmol. .698. 2 R S S S S S 1 S.668.40–9. 2 R R R R R R 1 S. complexesa Catalyst 1 Substrate 1-octene 1-hexene styrene 4-Cl styrene 4-NO 2 styrene 1. The substituted ethylenediamine Table 2 Data for enantioselective epoxidation of prochiral non-functionalised olefins catalyzed by symmetrical chiral NiŽII.2 dihydronaphthalene 1-octene 1-hexene styrene 4-Cl styrene 4-NO 2 styrene 1. as indicated by the angle between the planes defined by atoms N1.438. 2 S R R R R R 1 S. O1 and O6 in the case of complex 1 Ž4.448 Ž in molecule B. While in the case of 2 and 4. C1. Ni. C19. This is evident from the dihedral angles between the mean planes defined by atoms N1. and 8. 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 24 % Conversionb 79 82 83 72 49 58 72 74 42 45 48 45 70 72 40 45 40 63 71 73 42 50 53 45 69 72 40 45 43 61 ee c 34 39 37 42 46 47 39 44 42 37 44 49 37 42 45 42 47 58 39 44 42 37 44 50 39 44 42 37 44 48 Configuration R R R R R 1 S. O6 with respect to the plane defined by atoms N1. C24. N2 and O1. C13. r Journal of Molecular Catalysis A: Chemical 160 (2000) 217–227 223 deviation of atoms ranging from " 0. solvent 1. 2 R S S S S S 1 R.2 dihydronaphthalene 1-octene 1-hexene styrene 4-Cl styrene 4-NO 2 styrene 1..218. at room temperature. C6.038 Žin molecule A.898 and 9. Apyrone 1B and Apyrone 2B planes are bent symmetrically. C23. O6 with respect to the plane N1. O6. is slightly more in the case of complex 1 Ž7. making angles 8.2 dihydronaphthalene 1-octene 1-hexene styrene 4-Cl styrene 4-NO 2 styrene 1.72–7.2 dihydronaphthalene 1-octene 1-hexene styrene 4-Cl styrene 4-NO 2 styrene 1. C8. All the complexes have a AsteppedB conformation with a slight twist in the ligand moiety. O1 and N2. with respect to the N2 O 2 plane. it is defined by atoms N1. Ni.. C1. C12. The twist angles between pyrone units are 12. C7. NaOCl Ž4 ml.248 with respect to one another in structures A and B. O6 Ž3.0 ml dichloromethane at pH s 11.I.998. Complexes 2 and 4 are isostructural with minor variations in the degree of non-planarity of the ligand and are not very different from complex 1.. The twist.R.. catalyst Ž0. b Determined by GC analysis.3. 6.040 to ˚ 0. O1. C25.2 dihydronaphthalene Time Žh.02 mmol.096 A. O1 and by N2. N2. than complex 2 and 4 Ž3..02–8. N2. C14. c Determined by chiraldex BPH and BDA. C30. Kureshy et al.74–4. In complex 1.

Moderate to low conversion was obtained in the case of 1. 2 dihydronaphthalene. O hydrogen bonding. S1 s 1-octene. This is further confirmed by the torsion angles of the substituted ethylenediamine collar moiety. 1-hexene.66Ž1. Data regarding the enantioselectivities are given in Table 2. including the imino nitrogen. The low stability of the crystals in open air for 2 Scheme 1. . The enantiomeric excess for the resulting epoxide separated by short column of silica gel was evaluated by chiral capillary column Žchiraldex BPH and BDA. S5 s 4-nitrostyrene. and 1. N1. S4 s 4-chlorostyrene. N2 with C10–C15 s 84.. 8x. The methyl group of the substituted ethylenediamine moiety is almost perpendicular to the coordination sphere. O1. r Journal of Molecular Catalysis A: Chemical 160 (2000) 217–227 and 4 may be due to the loosely bound acetonitrile molecules present as solvent of crystallization in the lattice. catalyst 1–5 and substrate S1–S6. 6. to give corresponding epoxide at pH s 11.84 for 2 and 83.318 and y0. 4-chlorostyrene.50Ž2. which is in gauche conformation wtorsion angles in A N1–C9–C10–N2 s 44. while in the case of styrene and 4-chlorostyrene. The molecules are stabilized in the crystal lattice by strong C–H . S3 s styrene. and plane Ni. In absence of the catalyst under similar reaction conditions.313 A. . A probable mechanism for catalytic reaction.232 A ˚ of C9 being y0.3.8 in molecule B N1X –C9X –C10X –N2X s 43. making the five-membered chelate ring in halfchair conformation. 3D view of % conversion to epoxide vs.. 6. 6. In the case of complexes 2 and 4.I. indi- Fig. N2 with C17–C22 s 86. The catalysts 1–5 were screened by GLC for enantioselective epoxidation of styrene. moiety is also buckled in opposite direction from the NiN1N2 plane with the displacement ˚ and C10 being 0.224 R. 1-octene. O1.2-dihydronaphthalene using NaOCl.92 for 2 and 87. The catalysts 1–5 gave excellent conversion with 1-octene and 1-hexene Ž 70–82%.43Ž1. N1.81Ž2.8 for 4. S2 s 1-hexene. . 4-nitrostyrene. this could be achieved with the catalyst 1.2-dihydronaphthalene with all the catalysts ŽFig. the fivemembered chelate ring.407 A in A and the corresponding displacements in ˚ molecule B.8 for 4.. Enantioselective epoxidation of nonfunctionalised alkenes. there is no reaction between oxidant and olefins. . which are 0. S6 s 1. Kureshy et al. adopts Ahalf chairB conformation in which phenyl rings are almost perpendicular to the coordination plane and are oriented in the opposite direction Žthe angle between plane Ni.

on the basis of repulsive steric interactions among the substituents on the salen ligand and alkenes..R. catalyst 1–5 and substrate S1–S6. therefore. the most plausible mechanism for the reaction would involve the formation of NiŽII. S1 s 1-octene. However. r Journal of Molecular Catalysis A: Chemical 160 (2000) 217–227 225 Fig.2 dihydronaphthalene.. . However. 7. one would expect 100% enantioinduction. though the chemical conversions were low in comparison to the long chain alkenes. Furthermore. reacts with the substrate to form an intermediate ŽC. 8. seems to be more dominating at intermediate stages responsible for oxygen atom transfer. S6 s 1. Different mode of approach of the substrate towards the catalyst-1.2-dihydronaphthalene Ž Fig. If the intermediate ŽD. Highly reactive oxo intermediate ŽB. complexes seem to extend their coordination number up to six at an intermediate stage to accommodate oxygen atom and substrate ŽScheme 1. 7. this is not the case Ženantiomeric excess 34–58%. experimentally. gave a powerful unified hypothesis and suggested pathway e with twisted salen geome- Fig. is to produce epoxide directly and the catalyst back. Kureshy et al. S2 s 1-hexene. cating indirectly the involvement of catalyst during our catalytic runs. During the catalytic reaction. S4 s 4-chlorostyrene. . Therefore. the better enantioinduction was in the case of 1. in order to understand the mechanism of metal-salen catalysed asymmetric epoxidation. rather than electronic.I. it is interesting to point out that for all catalysts. proposed approaches a and b ŽFig. Jacobsen et al.. Further. oxo intermediate at first step.. S5 s 4-nitrostyrene. where fast rotation of C–C bond on alkene and Ni–O bond between metal complex and olefin get precedence over collapse step responsible for the formation of product epoxide. the square planar NiŽII. 8. 3D view of % ee ’s to epoxide vs. The steric consideration. . which on rearrangement gives oxametallocyclic intermediate Ž D. While Katsuki et al. Houk et al. recently. S3 s styrene. suggested pathway c along nitrogen–manganese bond axis based on the repulsive p-electron interactions between ligand and substrate p-electrons. These results can be explained on the basis of formation of another intermediate of free radical nature ŽE.

Am. Brauman. Pietikainen.2 S-Ž q. Bioinorganic Catalysis.H. Chem....-1.. Teyklar ` ŽEds. Tetrahedron Lett. NY. p. Synlett Ž1994. Karlin. De Vries. w25x O. Marcell Dekker. Enantiomeric excess of the epoxide formed was better in the case of 1. w18x K. Catal. 1993. 1 S. w26x R. Khan.A. Tetrahedron: Asymmetry 4 Ž1993. Burrows. N.H. Martell. Kureshy et al. Tetrahedron 52 Ž1996.. Chem. Koola. Kureshy. Ed. B.A. 481. Collman. 26 Ž1987. C. 1974. Adam. McCormick. Irie. Gelling.N. Chem. Ito. -diphenyldiamino ethane. Soc.H.I.. 81. Nagata.I. Metal-catalysed oxidations of organic compounds.F. 110 Ž1996. 319. J. Am.. w5x E. p. Katsuki. Academic Press. Matsomoto. Palucki. Lee.. K. A. Uffelman. 6124. NY. Tetrahedron Lett.2 S-Žq.J. with 3-acetyl 4-hydroxy 6-methyl 2-pyrone were investigated as catalysts for the enantioselective epoxidation of 1-hexene. J. Zhang. 1993. 1 R . Feringa. Yamada. K. w16x O.I. Noda. where the enantioselection is provided by the chiral environment set up by transmission through Salen ligand of the effect of the stereogenic carbon w38x. N.. 1. 4-nitrostyrene and 1. Angew. Kochi.F..J. 159. Yoon. Catal. Irie. Am. C. D. 1-octene. styrene. 89 Ž1989.E. Academic Press. Zang. NY. Chem. Noda. Abdi. 117. 3669. w15x G. 7 therein. Y. J. Barton. M. 1 S. w17x O. 30 Ž1991. T. Wagler. J. Imagawa. Jacobsen..H. Hence. E. NY. NY. Burrows. J. Tetrahedron Lett.P. 403.226 R. VCH. 110 Ž1988. 1993. Ž1993. Metalloporphyrins in Catalytic Oxidation. V. Bhatt.K. Soc. Katsuki.H. Kochi. 32 Ž1991. 255. Plenum. NY.J.R. 1693. NY. The Activation of Dioxygen and Homogenous Catalytic Oxidation. Jacobsen. Hayaishi ŽEd. Bhatt. T. Mol. Loebach. Catalytic Asymmetric Synthesis. Rev. Bioinorganic Chemistry of Copper. A. T. the NiŽ II. C. Mukaiyama.I. Excellent conversions were obtained with long chain alkenes than other non-functionalised alkene. w23x H.. Int. 4-chloro-. 112 Ž1990. w27x R. References w1x R. ¨ w14x W. J.. Inorg. Kureshy. Wilson. M. w12x R. Conclusions Square planar chiral NiŽ II. therefore. This can be one of the reasons for these complexes not showing desirable enantioselection besides the factors explained in Scheme 1. Hosoya. Lett. w7x Y. Chem. Ojima ŽEd. Jørgensen. Sawyer ŽEds. Sebok. 908. 1404. 241. Kinneary.2-dihydronaphthalene. T. w22x J. Tetrahedron Lett. E. Chem. which infers that the steric consideration rather than electronic.K.A. 29 Ž1988.-diamino cyclohexane. S. Naruta. p. J. C. 33. Mol. 4087. Science 261 Ž1993.2 RŽy.R. A. w21x J. Nemes. Reedijk ŽEd. X. Chem.K. 3521. Acknowledgements RIK and NHK are thankful to CSIR.2 R-Ž y . 877. -diphenyldiamino ethane.R.R. 8.H.M. w2x K. 96 Ž1995. r Journal of Molecular Catalysis A: Chemical 160 (2000) 217–227 try. Academic Press. -diamino cyclohexane. Patonay. w11x T. 1 R .D. Chap. Hayaishi ŽEd. PI is also thankful to CSIR for providing Senior Research Fellowship. Meetsma. Bolhuis.R. w4x C. T. Chem. Sheldon. and Ref. Ito. S. 1994. N. p. Soc.L. 2801. Rispens. 110 Ž1988. K. Katsuki. 1981.J. 36 Ž1995. N. w24x J. Burrows.S.2-diaminopropane. it seems to be more dominating at intermediate stage responsible for oxygen atom transfer. w9x R. T.T. Meunier. A. w6x J. Khan. w19x D. T. J. J. Chapmann & Hall. salen complex. 1962. w13x P. cial assistance. A.L. 5457. Jeko. although the steric requirements are not sufficient in order to define the specific pathway except for the methyl group on azomethine carbon offering some resistance on path d ŽFig. J. 1411. Schiff base complexes derived from S-Žq. Y. Abdi. 36 Ž1995.J. Abdi. Tetrahedron: Asymmetry 2 Ž1991.N. 1055. w3x B. Bolm. 431. it would be desirable to introduce more steric constrains on the pyrone rings in order to achieve better enantioselection. Z. Engl. J. Jacobsen.S. In the present case.N. in: R.N. 327. E.R. w28x R. P. w8x W.T.V. N. S. 1993. Levai. 36 Ž1995. Khan. Kinneary. Tetrahedron Lett.D. Kureshy.. Molecular Mechanics of Oxygen Activation. Irie. salen complex is conformationally very similar to that of MnŽIII.H. DST and Third World Academy of Science for finan- . K.. w10x R. Oxygenases.J.2dihydronaphthalene in the present study in the presence of NaOCl as oxidant. 7. 92 Ž1992. NY. Albert. S. w20x J. in: I. Marcel Dekker. Rev. F.H. Sheldon ŽEd. 8..I.

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