2920
Y.-C. Cheng, S.-W. Tsai / Tetrahedron: Asymmetry 15 (2004) 2917–2920
and enantioselectivity as well as thermal stability for
producing the desired (R)-ester at any specific temper-
ature.
References and notes
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hedron: Asymmetry 2000, 11, 4781–4790.
4. Experimental
4.1. General remarks for analytical procedure
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The esterification of (RS)-2-(4-chlorophenoxy)propionic
acid with various alcohols was monitored by HPLC
using a chiral column (Chiralcel OD-H, Daicel Chemical
Industries) capable of separating the internal standard
of acetophenone, (R)- and (S)-ester with the retention
time and composition of mobile phase given in Table 5.
A flow rate of 1.0 mL minÀ1 with UV detection at
270 nm was used for quantification at the column tem-
perature of 25 ꢀC.
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Table 5. Retention time and composition of mobile phase
Alcohol
n-Hexane:isopro-
panol:acetic acid
(v/v)
Retention time (min)
Aceto-
phenone
(R)-Ester (S)-Ester
n-Propyl97:3:1
n-Butyl100:0.6:0
n-Hexyl100:0:0
8.75
12.3
21.1
6.7
8.8
7.8
11.1
17.8
13.3
21.1
Trimethylsilyl- 100:0:0
methyl
12.4
16.1
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4.2. General procedure for enantioselective esterification
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(RS)-2-(4-Chlorophenoxy)propionic acid, alcohols and
organic solvents at the highest purity are commercially
available. A Candida rugosa lipase (Lipase MY, 30
units/mg of solid) was provided by Meito Sangyo
(Tokyo, Japan). The crude papain (P-3375, Sigma) was
dissolved at first in deionized water at 4 ꢀC, centrifuged
to collect the precipitate and then lyophilized in vacuum
to obtain the crude Carica papaya lipase (CPL). To
3 mL of anhydrous cyclohexane were added 15 mM of
alcohol, 1.8 mM of (RS)-2-(4-chlorophenoxy)propionic
acid and 3 mg of CPL at 45 ꢀC. Samples were withdrawn
and injected onto the HPLC at different time intervals,
from which conversions, enantiomeric excesses for the
(R)-ester and enantiomeric ratios (i.e. E value, defined as
the ratio of initialrates for both substrates) were
determined. Similar experiments were carried out by
changing the solvent, temperature or Lipase MY.
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Acknowledgements
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The financialsupport from the Chinese NationalScience
Councilwith Grant NSC92-2214-E-006-011 is appreci-
ated.