Enantiomerically pure allylic alcohols: preparation by Candida parapsilosis ATCC 7330 mediated deracemisation

Article abstract of DOI:10.1016/j.tetasy.2008.07.012

Biocatalytic deracemisation of racemic allylic alcohols by whole cells of Candida parapsilosis ATCC 7330 resulted in the formation of the (R)-enantiomers in high enantiomeric excesses (up to >99%) and isolated yields (up to 79%).

Full text of DOI:10.1016/j.tetasy.2008.07.012

Tetrahedron: Asymmetry 19 (2008) 1698–1701
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Tetrahedron: Asymmetry
journal homepage: www.elsevier.com/locate/tetasy
Enantiomerically pure allylic alcohols: preparation by
Candida parapsilosis ATCC 7330 mediated deracemisation
Devamani Titu a, Anju Chadha a,b,
*
a Laboratory of Bioorganic Chemistry, Department of Biotechnology, Indian Institute of Technology Madras, Chennai 600 036, India
b National Center for Catalysis Research, Indian Institute of Technology Madras, Chennai 600 036, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Biocatalytic deracemisation of racemic allylic alcohols by whole cells of Candida parapsilosis ATCC 7330
resulted in the formation of the (R)-enantiomers in high enantiomeric excesses (up to >99%) and isolated
yields (up to 79%).
Received 27 May 2008
Accepted 8 July 2008
Available online 26 July 2008
Ó 2008 Elsevier Ltd. All rights reserved.
1. Introduction
of racemic aryl a- and b-hydroxy esters to the corresponding enan-
tiomerically pure (S)-hydroxy esters in high chemical yields (up to
85%) and up to >99% ee by Candida parapsilosis ATCC 7330 has
previously been reported by our group.16 These esters include
(3E)-alkyl-2-hydroxy-4-arylbut-3-enoates,16e (3E,5E)-alkyl-2-hy-
droxy-6-arylhexa-3,5-dienoates16g and (3E)-alkyl-4-(hetero-2-yl)-
2-hydroxybut-3-enoates.16h Extending the substrate specificity of
the biocatalyst, herein we report for the first time, the C. parapsilo-
sis ATCC 7330 mediated deracemisation of allylic alcohols in high
enantiomeric excess (up to >99%) and yields (up to 79%).
Chiral allylic alcohols have attracted considerable attention due
to their stereodirecting propensity in diastereoselective reactions.1
They are considered valuable substrates for both synthetic2 and
mechanistic investigations.3 These important chiral synthons are
used for the synthesis of pharmaceuticals such as verapamil4 and
baclofen.5 Several methods, chemical6 and enzymatic,7 have been
reported for the synthesis of these compounds. Enantiopure 4-phe-
nyl-but-3en-2-ol can be obtained either by kinetic resolution of the
rac-alcohol employing Sharpless epoxidation8 or via asymmetric
hydrogenation of the corresponding ketone.9 Metal catalysed
hydrogen-transfer protocols are not very successful due to insuffi-
cient chemodifferentiation between C@C and C@O double bonds.10
To circumvent this limitation of selectivity, enzymes are
recognised to be amongst the most effective catalysts. Biocatalytic
preparation of enantiomerically pure allylic alcohols by lipase
mediated resolution of racemic allylic alcohols11 and biocatalytic
asymmetric reduction of the precursor prochiral ketones is
known.12 The asymmetric reduction of (3E)-phenyl-but-3en-2-
one to enantiomerically pure (2S,3E)-4-phenyl-3-butene-2-ol
(>99% ee) by secondary alcohol dehydrogenase from Thermoanae-
robacter ethanolicus is reported,13 but whole cells are preferred
over isolated enzymes as the need for additional expensive cofac-
tors is unnecessary. Enzymatic resolution is a widely used method
but it results in 50% of the unwanted enantiomer unlike biocata-
lytic deracemisation which ideally gives only one enantiomer in
high enantiomeric excess and chemical yield.14 Dynamic kinetic
resolution of (3E)-4-phenyl-3-butene-2-ol resulted in (2R,3E)-4-
phenyl-3-butene-2-ol in high enantiomeric excess and yield, but
a toxic metal catalyst is used for the racemisation and the time
taken for the entire process is more than 24 h.15 Deracemisation
2. Results and discussion
2.1. Synthesis of racemic allylic alcohols 2a–2j
Racemic allylic alcohols 2a–2j were synthesised by the conden-
sation of an aldehyde with acetone17 followed by sodium borohy-
dride reduction with methanol7c (Scheme 1).
2.2. Deracemisation of racemic allylic alcohols 2a–2j using
C. parapsilosis ATCC 7330
Deracemisation of racemic allylic alcohols by whole cells of C.
parapsilosis ATCC 7330 was standardised using (3E)-4-phenyl-3-
butene-2-ol 2a as the substrate. The (R)-enantiomer of the product
was obtained in 99% ee and 75% yield. To prove the generality of
this deracemisation reaction with respect to the substrate struc-
ture, a variety of aryl substituted allylic alcohols were deracemised
using C. parapsilosis ATCC 7330 (Scheme 2), which resulted in the
formation of their (R)-enantiomers in >76–99% ee and 68–79%
yields. Substrates with different para-substituents (Table 1, entries
2b, 2d and 2f) on deracemisation gave 98–99% ee and 70–79%
isolated yields of their corresponding (R)-enantiomers (Table 2).
In the case of the para-substituents irrespective of the
* Corresponding author. Tel.: +91 44 2257 4106; fax: +91 44 2257 4102.
E-mail addresses: anjuc@iitm.ac.in, anjuchadha@hotmail.ac.in (A. Chadha).
0957-4166/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2008.07.012

D. Titu, A. Chadha / Tetrahedron: Asymmetry 19 (2008) 1698–1701
1699
O
OH
O
O
NaBH4, MeOH
R
R
0-25ºC, 2h
R
H
aq NaOH, 4h
Yield - 70-90%
Yield - 65-90%
2a - 2j
1a - 1j
R = Ph, o-CH3Ph, p-CH3Ph, o-CH3OPh, p-CH3OPh, o-ClPh, p-ClPh, o,p-ClPh, C10H7 and C14H9
Scheme 1. Synthesis of racemic allylic alcohols 2a–2j.
OH
OH
Candida parapsilosis ATCC 7330
R
R
º
H2O, 3h , 25 C
"R"
ee - 76-99%
2a - 2j
Yield - 68-79%
3a - 3j
R = Ph, o-CH3Ph, p-CH3Ph, o-CH3OPh, p-CH3OPh, o-ClPh, p-ClPh, o,p-ClPh, C10H7 and C14H9
Scheme 2. Deracemisation of racemic allylic alcohols 2a–2j using whole cells of Candida parapsilosis ATCC 7330.
Table 1
Synthesis of racemic allylic alcohols 2a–2j
Table 3
Retention times of enantiomerically pure allylic alcohols 3a–3j
Entry
R
Yield (%)
Entry
R
Elution of HPLC peaks
Retention time in min
Column
2a
2b
2c
2d
2e
2f
2g
2h
2i
Ph
p-MeC6H4
o-MeC6H4
p-MeOC6H4
o-MeOC6H4
p-ClC6H4
90
89
80
90
75
78
72
70
85
76
Minor
Major
3a
3b
3c
3d
3e
3f
3g
3h
3i
Ph
p-MeC6H4
o-MeC6H4
p-MeOC6H4
o-MeOC6H4
p-ClC6H4
18.5
14.0
12.1
14.0
13.3
12.2
9.9
20.9
16.2
13.2
16.0
15.2
14.2
11.0
8.2
OJ-H
OJ-H
OJ-H
OJ-H
OJ-H
OJ-H
OJ-H
OJ-H
OJ-H
OJ-H
o-ClC6H4
o,p-Cl2C6H3
1-Naphthyl (C10H7)
9-Anthranyl (C14H9)
o-ClC6H4
2j
o,p-Cl2C6H3
1-Naphthyl (C10H7)
9-Anthranyl (C14H9)
6.2
19.3
20.1
23.2
22.2
3j
Table 2
Deracemisation of allylic alcohols 2a–2j using whole cells of Candida parapsilosis ATCC
7330
electronic nature of the substituents (methyl, chloro and methoxy),
the ee of the deracemised product remained very high (98–99%).
Substrates generated from the standard substrate 2a with an ortho
substituent (Table 1, entries 2c, 2e and 2g) showed a slight
decrease in the (92–95%) of the product. Substrates with bulky
groups, for example, (3E)-4-(naphthalen-2-yl)but-3-en-2-ol, 2i
and (3E)-4-(anthracen-2-yl)but-3-en-2-ol, 2j gave poor ee whilst
the disubstituted (3E)-4-(dichlorophenyl)but-3-en-2-ol (Table 1,
entry 2h) on deracemisation gave 90% ee and 68% yield of its
(R)-enantiomer.
Entries
R
ee (%)a
Yield (%)
2a
2b
2c
2d
2e
2f
2g
2h
2i
Ph
p-MeC6H4
o-MeC6H4
p-MeOC6H4
o-MeOC6H4
p-ClC6H4
>99
98
95
>99
94
>99
92
90
76
10
75
72
73
70
69
79
70
68
71
78
o-ClC6H4
o,p-Cl2C6H3
1-Naphthyl (C10H7)
9-Anthranyl (C14H9)
2j
The absolute configuration of the enantiomerically pure enantio-
mers was assigned to be (R) by comparing the specific rotations
a
Enantiomeric excess was determined by Chiral HPLC.
Hydroxy
Priority
Priority
1
OH
R
OH
1
OH
R = COOR1
Candida parapsilosis
O
R = Me
Ar
Ar
R1
2
3
Ar
Candida parapsilosis
2
3
O
ATCC 7330
ATCC 7330
(R)
(S)
Alkyl/
Ester/
Other?
Substituted
Allyl group
Scheme 3. Deracemisation of allylic alcohols and a-hydroxy enoates by Candida parapsilosis ATCC 7330.

1700
D. Titu, A. Chadha / Tetrahedron: Asymmetry 19 (2008) 1698–1701
with the literature data.18 The elution profile from HPLC was found
to be generally in the following order; the (S)-enantiomer is the
early eluting enantiomer whilst the (R)-enantiomer is the late
eluting enantiomer (Table 3). The deracemisation of allylic alcohols
by C. parapsilosis ATCC 7330 possibly follows a stereoinversion
mechanism,19 that is, enantioselective oxidation of one antipode
fied by column chromatography using hexane/ethyl acetate (95:5)
as eluent. The same procedure was followed for all the compounds
1b–1j (Scheme 1).
4.2.2. Synthesis of racemic allylic alcohols (2a–2j). Typical
procedure for the (3E)-4-phenyl-3-butene-2-ol 2a
to the ketone intermediate, followed by
a
complementary
Reduction of (3E)-4-phenyl-3-butene-2-one 1a (benzylidene
acetone 2.04 g, 0.014 mol) (Scheme 1) was carried out with sodium
borohydride (0.56 g, 0.015 mol) in methanol (5 ml) for 2 h at 0–
10 °C. After completion of the reaction, the reaction mass was neu-
tralised with dilute HCl (5%) and extracted with ethyl acetate. The
organic layer was dried over Na2SO4 and evaporated under vac-
uum. Compound (3E)-4-phenyl-3-butene-2-ol 2a was obtained as
colourless oil in 90% yield (1.9 g) after column purification using
hexane/ethyl acetate (90:10) as solvent. The same procedure was
followed for the synthesis of all racemic allylic alcohols 2b–2j
(Scheme 1, Table 1).
enantioselective reduction of the intermediate ketone to give a
single enantiomer in high yield and ee. The formation of a ketone
intermediate was confirmed by the time course of the deracemisa-
tion of racemic (3E)-4-phenyl-3-butene-2-ol 2a, as monitored by
HPLC using a reverse phase column. Aliquots of the reaction mix-
ture were taken every 15 min for 3 h. The ketone intermediate
was detected at 30 and 45 min. Deracemisation of allylic alcohols
using whole cells of C. parapsilosis ATCC 7330 yielded the
(R)-enantiomer whilst the
a
- and b-hydroxy enaotes16 gave the
(S)-enantiomer on deracemisation due to the differences in the
prioritisation of the groups for assigning the (R)- and (S)-configura-
tions (Scheme 3).
4.3. Growth conditions for C. parapsilosis ATCC 7330
C. parapsilosis ATCC 7330 was procured from ATCC 7330, which
was grown in yeast malt broth medium (50 ml) in 250 ml
Erlenmeyer flasks incubated at 25 °C, 200 rpm. The cells were
harvested by centrifuging the 44 h culture broth at 4500 rpm for
15 min and subsequent washing with sterile water. The process
was repeated three times, and the wet cells were used for
biotransformation.16b
3. Conclusion
We have developed a one-pot biocatalytic method for the der-
acemisation of allylic alcohols using whole cells of C. parapsilosis
ATCC 7330 to give the (R)-allylic alcohols in good yields (68–
79%) and high enantiomeric excesses (76–99%) under mild reaction
conditions. This method is better than all the reported methods so
far, as the biocatalyst shows high enantioselectivity towards race-
mic allylic alcohols and the entire deracemisation process takes
less than 3 h. With appropriate immobilisation of the biocatalyst,
this method can be suitably scaled up.
4.4. A typical procedure for the deracemisation reaction of
(3E)-4-phenyl-3-butene-2-ol 2a using the whole cells of C.
parapsilosis ATCC 7330
To a 250 ml conical flask containing 48g of pelleted C. par-
apsilosis ATCC 7330 cells suspended in 44 ml of sterile distilled
water, 144 mg (0.97 mmol) of (3E)-4-phenyl-3-butene-2-ol 2a
dissolved in 3.2 ml of ethanol was added. The reaction was car-
ried out in a water bath shaker at 150 rpm and 25 °C for 3 h.
After incubation, the reaction mixture was centrifuged at
5000 rpm for 10 min. The product formed was isolated using
ethyl acetate (3 ꢀ 30 ml) and the organic layer was dried over
anhydrous sodium sulfate. The solvent was removed by evapora-
tion and the enantiomerically pure (2R,3E)-4-phenyl-3-butene-2-
ol 3a was obtained as a colourless solid after purification by
silica gel column chromatography using hexane/ethyl acetate
(90:10) as a mobile phase eluent. The ee was found to be 99%,
as determined using HPLC. The yield of the isolated product,
(2R,3E)-4-phenyl-3-butene-2-ol 3a was 75% (108 mg). Mp
4. Experimental
4.1. General methods
1H and 13C NMR spectra were recorded in CDCl3 solution on a
Bruker AV-400 spectrometer operating at 400 and 100 MHz,
respectively. Chemical shifts are expressed in ppm values using
TMS as an internal standard. HPLC analysis was carried out on a
Jasco PU-1580 liquid chromatograph with a PDA detector using
Chiralcel OJ-H chiral columns (Daicel, 4.6 ꢀ 250 mm). Hexane/iso-
propanol was used as the mobile phase, however, the proportion of
solvents and the flow rate varied for different compounds. Optical
rotations were recorded on a Jasco Dip 370 digital polarimeter. TLC
was carried out on Kieselger 60 F254 aluminium sheets
(Merck1.05554). All other chemicals used were of analytical grade
and distilled before use. C. parapsilosis ATCC 7330 was purchased
from ATCC Manassas, VA 201018, USA. All chemicals for media
preparation were purchased locally. All substrates were synthes-
ised as shown in the given schemes.
57–59 °C; ½a 2D5
¼ þ33:2 (c 1.02 CHCl3); Spectroscopic data were
ꢁ
identical to those reported in literature.7e Racemic allylic alco-
hols 2b–2j were also used as substrates in the same manner
(Scheme 2 and Table 2).
4.5. Spectroscopic characterisation of the deracemised allylic
alcohols (3b–3j)
4.2. Synthesis of substrates
4.2.1. Preparation of various aryl substituted but-3en-2one 1a–
1j: Typical procedure for the compound (3E) phenylbut-3en-
2one 1a
4.5.1. (2R,3E)-4-(4-Methylphenyl)-3-buten-2-ol 3b
Colourless oil; ½a D25
¼ þ20:9 (c 0.8, CHCl3); Spectroscopic data
ꢁ
identical to that reported in the literature.18b
The aldehyde (43.2 mmol) was added gradually to a solution of
NaOH (2.2 g) in H2O (20.0 ml) and ketone (43.3 mmol) in ethanol
(12 ml) at 0 °C. The reaction mass was stirred at room temperature
for 4 h. After 4 h, satd NH4Cl solution was added to the flask, fol-
lowed by extraction with ether. The combined organic layers were
dried over Na2SO4 and concentrated to give a solid which was
washed successively with hexane to give pure enones. (3E)-Phen-
ylbut-3en-2one 1a was obtained as a yellow solid after being puri-
4.5.2. (2R,3E)-4-(2-Methylphenyl)-3-buten-2-ol 3c
Colourless oil; ½a D25
¼ þ15:4 (c 1.1, CHCl3); Spectroscopic data
ꢁ
identical to that reported in the literature.20a
4.5.3. (2R,3E)-4-(4-Methoxyphenyl)-3-buten-2-ol 3d
Colourless oil; ½a D25
¼ þ9:4 (c 1.1, CHCl3); Spectroscopic data
ꢁ
identical to that reported in the literature.20c

D. Titu, A. Chadha / Tetrahedron: Asymmetry 19 (2008) 1698–1701
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1701
4.5.4. (2R,3E)-4-(2-Methoxyphenyl)-3-buten-2-ol 3e
Colourless oil; ½a D25
¼ þ6:4 (c 1.02, CHCl3); Spectroscopic data
ꢁ
4. Brenna, E.; Fuganti, C.; Graselli, P.; Serra, S. Eur. J. Org. Chem. 2001, 2001, 1349.
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4.5.5. (2R,3E)-4-(4-Chlorophenyl)-3-buten-2-ol 3f
Colourless solid; mp 60–62 °C; ½a D25
¼ þ28:1 (c 1.02, CHCl3);
ꢁ
Spectroscopic data identical to that reported in the literature.7e
4.5.6. (2R,3E)-4-(2-Chlorophenyl)-3-buten-2-ol 3g
Colourless oil; ½a D25
ꢁ
¼ þ8:3 (c 0.70, CHCl3); 1H NMR (400 MHz,
CDCl3) dH 1.29–1.31 (3H, d, J = 6.4 Hz), 2.02 (1H, sb), 4.42–4.45
(1H, m), 6.13–6.19 (1H, dd, J1 = 15.8 Hz, J2 = 6.3 Hz), 6.84–6.88
(1H, d, J = 15.8 Hz), 7.06–7.12 (2H, m), 7.24–7.26 (1H, d,
J = 7.6 Hz), 7.42–7.44 (1H, d, J = 7.6 Hz); 13C NMR (100 MHz, CDCl3)
dC 23.3, 68.8, 125.5, 126.8, 127.5, 128.6, 129.6, 133.1, 134.8, 136.3;
8. Martin, V. S.; Woodward, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K.
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IR mmax (neat): 3334, 2970, 2362, 1650, 1470, 1033, 1049 cmꢂ1
,
HRMS (ESI): found 183.0571, C10H12OCl [M+H]+ requires
183.0577.
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4.5.7. (2R,3E)-4-(2,4-Dichlorophenyl)-3-buten-2-ol 3h
Colourless oil; ½a D25
ꢁ
¼ þ4:6 (c 0.5 CHCl3); 1H NMR (400 MHz,
CDCl3) dH 1.38–1.39 (3H, d, J = 6.4 Hz), 2.36 (1H, sb), 4.51–4.54
(1H, m), 6.20–6.26 (1H, dd, J1 = 16.4 Hz, J2 = 6.4 Hz), 6.86–6.90
(1H, d, J = 16.4 Hz), 7.18–7.46 (1H, d, J = 8Hz), 7.36 (1H, s), 7.44–
7.46 (1H, d, J = 8Hz); 13C NMR (100 MHz, CDCl3) dC 23.2, 68.7,
124.4, 127.1, 127.5, 129.3, 133.4, 133.5, 136.9, 136.8; IR mmax
(neat): 3338, 2970, 1650, 1585, 1469, 1048 cmꢂ1, HRMS (ESI):
found 217.0194, C10H10OCl2 [M+H]+ requires 217.0187.
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Priya, K.; Chadha, A. Tetrahedron 2005, 61, 12296; (f) Padhi, S. K.; Titu, D.;
Pandian, N. G.; Chadha, A. Tetrahedron 2006, 62, 5133; (g) Thangavel, V.;
Chadha, A. Tetrahedron 2007, 63, 4126; (h) Vaijayanthi, T.; Chadha, A.
Tetrahedron: Asymmetry 2007, 18, 1077; (i) Titu, D.; Chadha, A. J. Mol. Catal.
B: Enzym. 2008, 52–53, 168.
17. Isleyen, A.; Dogan, O. Tetrahedron: Asymmetry 2007, 18, 679.
18. (a) Sgala, S.; Fabrizi, G.; Cirilli, R.; Macone, A.; Bonamore, A.; Boffi, A.; Cacchi, S.
Tetrahedron: Asymmetry 2007, 18, 2791; (b) Tiecco, M.; Testaferri, L.; Santi, C.;
Tomassini, C.; Bonini, R.; Marini, F.; Bagnoli, L.; Temperini, A. Org. Lett. 2004, 6,
4751; (c) Nakamura, Y.; Egami, H.; Matsumoto, K.; Uchida, T.; Katsuki, T.
Tetrahedron 2007, 63, 6383.
4.5.8. (2R,3E)-4-(Naphtha1en-2-yl)-3-buten-2-ol 3i
Colourless oil; ½a D25
¼ þ7:2 (c 2.0 CHCl3); Spectroscopic data
ꢁ
identical to that reported in the literature.7e
4.5.9. (2R,3E)-4-(Anthracen-9-yl)-3-buten-2-ol 3j
Yellow colour solid; mp 98–103 °C; ½a D25
ꢁ
not determined; 1H
NMR (400 MHz, CDCl3) dH 1.48–1.50 (3H, d, J = 6.4 Hz), 4.47–4.73
(1H, m), 6.04–6.09 (1H, dd, J1 = 16.2 Hz, J2 = 6.29 Hz), 7.25–7.29
(1H, d, J = 16.2 Hz), 7.39–7.41 (4H, m), 7.91–7.94 (2H, m), 8.18–
8.21 (2H, m), 8.31 (1H, s); 13C NMR (100 MHz, CDCl3) dC 23.7,
69.1, 124.9, 125.0, 125.3, 125.7, 126.3, 128.6, 129.4, 131.3, 132.1,
142.2; IR mmax (neat): 3339, 2969, 2924, 1670, 1442 cmꢂ1, HRMS
(ESI): found 271.1099, C18H16O [M+Na]+ requires 271.1099.
Acknowledgements
We thank the Sophisticated Analytical Instrumentation Facility
(SAIF), and Department of Chemistry IITM for the NMR and Mass
analysis.
19. Strauss, U. T.; Faber, K. In Enzymes in Action Green Solutions for Chemical
Problems; Zwanenburg, B., Mikolajczyk, M., Kielbasinski, P., Eds.; Kluwer
Academic: Dordrecht, The Netherlands, 2000; pp 1–23. ch. 1.
20. (a) Catellani, M.; Deledda, S.; Ganchegui, B.; Henin, F.; Motti, E.; Muzart, J. J.
Organomet. Chem. 2003, 687, 473; (b) Biraman, V. B.; Jiang, H. Org . Lett. 2005, 7,
3445; (c) Wang, D.; Chen, D.; Haberman, J. X.; Li, C. J. Tetrahedron 1998, 54,
5129.
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