Page 105 - Catalysts for Fine Chemical Synthesis Vol 1 - Robert & Poignant

unfunctionalized alkenes a, b-unsaturated esters 91

6.1.2 EPOXIDATION OF (Z)-ETHYL CINNAMATE [4]

(S,S) catalyst (6 mol%) O
+ NaOCl(aq)
Ph CO 2 Et CH 2 Cl 2 Ph CO 2 Et
4-phenyl pyridine N-oxide
(1S,2S)

Materials and equipment

. Jacobsen's catalyst (S,S)-(ÿ)-N,N -bis(3,5-di-tert-butylsalicylidene)-1,2-
0
cyclohexane diaminomanganese(III) chloride, 98 %), 108 mg, 0.166 mmol,
6.5 mol%
. (Z)-Ethyl cinnamate, 500 mg, 2.55 mmol
The (Z)-ethyl cinnamate was obtained by hydrogenation of ethyl phenyl
propiolate using Lindlar's catalyst (5 % palladium on calcium carbonate,
poisoned with lead) in n-hexane under an atmospheric pressure of hydrogen.
The mixture, containing 75 % of the (Z)-ethyl cinnamate, 22 % of the over-
reduced alkane and 3 % of the (E)-ethyl cinnamate, was used without further
purification. 666 mg of this mixture contains 500 mg of (Z)-ethyl cinnamate
(2.55 mmol).
. 4-Phenylpyridine N-oxide, 116 mg, 0.680 mmol, 0.25 eq
. Sodium hydrogenphosphate aqueous solution 0.05 M, 10 mL
. Bleach (sodium hypochlorite, available chlorine 14 %), 5 mL
. Sodium hydroxide solution, 1 M
. Hydrogen chloride solution, 1 M
. Dichloromethane, petroleum ether, diethyl ether, tert-butyl methyl ether,
ethyl acetate
. Celite 1
. Brine
. Sodium sulfate
. Silica gel 60 (0.063±0.04 mm)
. p-Anisaldehyde

. 100 mL Flask with a magnetic stirrer bar
. Magnetic stirrer
. Beaker, 100 mL
. Separating funnel, 250 mL
. Rotary evaporator
. pH-meter