Page 88 - Catalysts for Fine Chemical Synthesis Vol 1 - Robert & Poignant
P. 88
74 hydrolysis, oxidation and reduction
lower than expected, the reaction should be repeated with tartrate distilled
under high vacuum and stored under vacuum or in an inert atmosphere.
. An anhydrous solution of 5.5 M of tert-butyl hydroperoxide in isooctane
stored over molecular sieves is available from Fluka.
. Liquid allylic alcohols ( (E)-2-methyl-3-phenyl-2-propenol and (E)-2-hexen-
Ê
1-ol) were stored over preactivated 3 A molecular sieves.
. Titanium isopropoxide needs to be manipulated carefully with gloves and
eye protection. If the yield and/or the enantiomeric excess is/are lower than
expected, the catalyst should be distilled under vacuum (b.p 78±79.5 8C,
1.1 mmHg).
5.2.1 EPOXIDATION OF CINNAMYL ALCOHOL [3,4]
Ti(O-iPr) 4 , (+)-DET O
Ph OH Ph OH
t-BuOOH, CH 2 Cl 2
( 2S,3S)
Materials and equipment
. l-()-Diisopropyl tartrate ( ()-DIPT), 400 mg, 2 mmol, 0.1 eq
Ê
. Dichloromethane stored over preactivated 3 A molecular sieves, 43 mL
Ê
. Activated powdered 4 A molecular sieves, 500 mg
. Titanium isopropoxide, 297 mL, 1 mmol, 0.05 eq
. Anhydrous solution of 5.5 M of tert-butyl hydroperoxide in isooctane stored
over molecular sieves, 5.5 mL, 30 mmol, 1.5 eq
. Cinnamyl alcohol, 2.68 g, 20 mmol
. Aqueous solution of sodium hydroxide 30 % saturated with sodium chloride,
6 mL
. Celite 1
. Brine
. Magnesium sulfate
. Silica gel 60 (0.063±0.04 mm)
. (R)-()-a-Methoxy-a-(trifluoromethyl)phenylacetyl chloride (MTPA chlor-
ide) or the (S)-enantiomer, 5 mg, 0.02 mmol
. 4-Dimethylaminopyridine (DMAP), 5 mg, 0.04 mmol
. Dichloromethane, diethyl ether, petroleum ether, ethyl acetate, n-hexane
. p-Anisaldehyde
. 50 mL Two-necked flask with a magnetic stirrer bar
. Magnetic stirrer
. Cooling bath (acetone/Dri-ice) equipped with contact thermometer, ÿ5 8C
. Bu Èchner funnel with glass frite (30 mL, porosity n83)
