Communications
was removed by rotary evaporator and the residue purified by flash
chromatography (silicagel 60, n-hexane: ethyl acetate 3:1 (v/v), Rf =
Catalytic Asymmetric Synthesis (Ed.: I. Ojima),Wiley-VCH,
New York, 1993,pp. 103 – 158.
[4] For reviews see: a) E. N. Jacobsen,M. H. Wu in Comprehensive
Asymmetric Catalysis, Vol. II (Eds.: E. N. Jacobsen,A. Pfaltz,H.
Yamamoto),Springer,Berlin, 1999,pp. 649 – 677; b) T. Katsuki
in Comprehensive Coordination Chemistry II, Vol. 9 (Eds.: J. A.
0.43) to give 5b (2.33 g,93%). M.p. 139.9 8C; [a]D25
=
+ 58.0 degcm3 gÀ1 dmÀ1 (c = 0.72 gcmÀ3,CH 2Cl2); IR (KBr): n˜ =
3338,3305,3086,3064,3028,2788,2713,1599,1494,1453,1348,
1324,1152; 1H NMR (400.13 MHz,CD Cl2): d = 1.6 (brs,1H,N H),
2
2.34 (s,3H,C H3),3.42 (d, J = 13.16 Hz,1H,C H2),3.60 (d, J =
McCleverty,T. J. Meyer),Elsevier Science,Oxford,
pp. 207 – 264.
2003,
13.16 Hz,1H,C H2). 3.74 (d,7.80 Hz,1H,C
HPh),4.27 (dd, J =
7.84 Hz,1H,C HPh),6.21 (brs,1H,N H),6.95–7.00 (m,4H,Ar),
[5] Y. Shi, Acc. Chem. Res. 2004, 37,488 – 496.
7.05–7.13 (m,5H,Ar),7.15–7.19 (m,5H,Ar),7.22–7.32 (m,3H,Ar),
7.37–7.39 ppm (m,2H,Ar);
[6] I. W. C. E. Arends, Angew. Chem. 2006, 118,6398 – 6400; Angew.
Chem. Int. Ed. 2006, 45,6250 – 6252.
13C NMR (75.47 MHz,CD 2Cl2): d =
21.56 (CH3),51.16 ( CH2),63.45 ( CHPh),67.22 ( CHPh),127.36,
127.48,127.69,127.92,127.94,128.04,128.34,128.40,128.76,128.77,
129.66,137.21,139.16,139.33,139.90,143.49 ppm; elemental analysis
calcd (%) for C28H28N2O2S: C 73.65,H 6.18,N 6.14,S 7. 02; found: C
[7] Y. Sawada,K. Matsumoto,S. Kondo,H. Watanabe,T. Ozawa,K.
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73.60,H 6.44,N 6.01,S 7.24. MS (CI,positive mode,isobutane)
457.3 [M+H]+(100),349(15),196 (40); HRMS (CI,negative mode,
isobutane) m/z: calcd for C28H27N2O2S: 455.1788 [MÀH]+;
found:455.1784.
m/z:
General protocol for Fe-catalyzed asymmetric epoxidation of
alkenes: Pyridine-2,6-dicarboxylic acid (4.24 mg, 0.025 mmol), ferric
[10] For an excellent review on the current status of Fe-catalyzed
organic reactions see: C. Bolm,J. Legros,J. Le Paih,L. Zani,
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chloride hexahydrate (6.76 mg,0.025 mmol),ligand
3, 4,or
5
(0.06 mmol),and the corresponding alkene 1 (0.5 mmol) were
mixed in 9 mL 2-methylbutane-2-ol and stirred at room temperature
for ca. 30 min.[24] The resulting mixture usually assumes pale yellow
color. When the yields and conversions were determined by GC,
100 mL dodecane was added as the internal standard. After samples
were removed for GC analysis,1 mmol of aqueous “30%” hydrogen
peroxide[25] dissolved in 1 mL 2-methylbutane-2-ol was added to the
reaction mixture over one hour using a syringe pump. In most cases
complete conversion was achieved after this time (GC or TLC
monitoring). For preparative purposes excess peroxide was destroyed
by adding 1 mL of a saturated aqueous solution of sodium sulfite and
shaking well. After addition of diethyl ether (10 mL) the organic
phase was separated. The aqueous phase was extracted with diethyl
ether (3 10 mL). The combined organic phases were dried over
anhydrous MgSO4. After filtration and solvent removal by rotary
evaporator,the crude product was either directly analyzed by chiral
HPLC or purified by silica gel chromatography on a short column
(hexane/ethylacetate 20:1,1% Et 3N) for full characterization.
[11] E. Rose,Q.-Z. Ren,B. Andrioletti, Chem. Eur. J. 2004, 10,224 –
230.
[12] For examples see: The Porphyrin Handbook: Synthesis and
Organic Chemistry, Vol. 1 (Eds.: K. M. Kadish,K. M. Smith,R.
Guilard),Academic Press,San Diego, 2000,chaps. 1–6,pp. 1 –
347.
[13] Q. F. Cheng,X. Y. Xu,W. X. Ma,S. J. Yang,T. P. You,
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[14] M. B. Francis,E. N. Jacobsen, Angew. Chem. 1999, 111,987 – 991;
Angew. Chem. Int. Ed. 1999, 38,937 – 941.
[15] M. Costas,A. K. Tipton,K. Chen,D.-H. Jo,L. Que,Jr.,
J. Am.
Chem. Soc. 2001, 123,6722 – 6723.
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Klawonn,G. Anilkumar,H. Jiao,C. Döbler,A. Spannenberg,W.
Mägerlein,H. Hugl,M. Beller, Chem. Eur. J. 2006, 12,1855 –
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Gelalcha,M. Beller, J. Organomet. Chem. 2006, 691,4419 – 4433;
d) S. Bhor,G. Anilkumar,M.-K. Tse,M. Klawonn,C. Döbler,B.
Bitterlich,A. Grotevendt,M. Beller, Org. Lett. 2005, 7,3393 –
3396.
Received: March 20,2007
Published online: July 12,2007
[17] G. Anilkumar,B. Bitterlich,F. G. Gelalcha,M. K. Tse,M. Beller,
Chem. Commun. 2007,289 – 291.
[18] C.-Y. Ho,Y.-C. Chen,M.-K. Wong,D. Yang, J. Org. Chem. 2005,
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2720.
Keywords: asymmetric catalysis · epoxidation ·
hydrogen peroxide · iron
.
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[24] The amounts of the iron salt,ligand ( S,S)-5b, H2pydic,H 2O2,and
solvent were proportionately doubled for epoxidation of 1i
(Table 3,entries 8 and 9).
[25] We used “30%” aqueous H2O2 (Merck) as received; the
peroxide content was determined by titration to range from
35% to 40%.
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