Enantioselective epoxidation of α,β-unsaturated ketones by phase-transfer catalysis using chiral quaternary ammonium salts

Article abstract of DOI:10.1081/SCC-120015774

The catalytic enantioselective epoxidation promoted by quaternary ammonium salt as a phase transfer catalyst is described. Treatment chalcone derivatives with sodium hypochlorite under mild reaction conditions afforded the corresponding epoxy ketones in g

Full text of DOI:10.1081/SCC-120015774

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Enantioselective Epoxidation of α,β-Unsaturated
Ketones by Phase-Transfer Catalysis Using Chiral
Quaternary Ammonium Salts
Dae Young Kim a , Young Jae Choi a , Hai Yoon Park a , Chang Ung Joung a , Kwang Oh Koh a
Joo Yang Mang a & Kang-Yeoun Jung b
,
a Department of Chemistry, Soonchunhyang University, Asan, Chungnam, Korea
b Department of Industrial Chemistry, Kangnung National University, Kangnung, Korea
Version of record first published: 17 Aug 2006.
To cite this article: Dae Young Kim, Young Jae Choi, Hai Yoon Park, Chang Ung Joung, Kwang Oh Koh, Joo Yang Mang &
Kang-Yeoun Jung (2003): Enantioselective Epoxidation of α,β-Unsaturated Ketones by Phase-Transfer Catalysis Using Chiral
Quaternary Ammonium Salts, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 33:3, 435-443
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 3, pp. 435–443, 2003
Enantioselective Epoxidation of a,b-Unsaturated
Ketones by Phase-Transfer Catalysis Using
Chiral Quaternary Ammonium Salts
1
1
Dae Young Kim,1, Young Jae Choi, Hai Yoon Park,
*
Chang Ung Joung,1 Kwang Oh Koh,1 Joo Yang Mang,1
and Kang-Yeoun Jung2
1Department of Chemistry, Soonchunhyang University,
Asan, Chungnam, Korea
2Department of Industrial Chemistry,
Kangnung National University, Kangnung, Korea
ABSTRACT
The catalytic enantioselective epoxidation promoted by quaternary
ammonium salt as a phase transfer catalyst is described. Treatment
chalcone derivatives with sodium hypochlorite under mild reaction
conditions afforded the corresponding epoxy ketones in good yields
with good to moderate enantiomeric excesses.
*Correspondence: Dae Young Kim, Department of Chemistry, Soonchunhyang
University, Asan, P.O. Box 97, Chungnam 336-600, Korea; Fax: +82-41-530-
1247; E-mail: dyoung@sch.ac.kr.
435
DOI: 10.1081/SCC-120015774
Copyright & 2003 by Marcel Dekker, Inc.
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436
Kim et al.
Key Words: Chiral ammonium salt; Enantioselective epoxidation;
Phase-transfer catalysis; a,b-unsaturated ketones.
The epoxide functional group is one of the most useful intermediates
in organic synthesis. Epoxides are versatile products and they easily
undergo stereospecific ring-opening reactions to form bifunctional com-
pounds and very important chiral building blocks in organic synthesis and
canbe used either as key intermediates inthe preparationof more complex
optically pure bioactive compounds.[1] This explains the great interest in the
development of methods for the synthesis of optically pure epoxides.[2]
The enantioselective epoxidation of a,b-unsaturated ketones has
been developed including the use of polyphasic systems involving hydro-
[3]
genperoxide inthe presence of polyamino acids,
alkylperoxides in
conjunction with lanthanoid–binaphtol complexes,[4] tartrate-modified
metal tert-butylperoxides,[5] and hydrogen peroxide in the presence of
chiral platinum(II) complexes.[6] Phase-transfer catalyzed reaction sys-
tems are one of the most useful methodologies for practical synthesis
because of the mild reaction conditions, safety, and operational simpli-
city.[7] The first example of asymmetric epoxidation under phase-transfer-
catalyzed conditions using electron deficient alkenes as the substrate was
reported by Wynberg et al.[8] in1976. High enantioselectivity for the
catalytic asymmetric epoxidationwas achieved using catalysts derived
from cinchona alkaloids.[9] Hereinwe report our ownresults onthe
efficient catalytic asymmetric epoxidation of chalcone and
its derivatives promoted by a new class of quaternary ammonium salts
derived from cinchonidine, which reacts as a phase-transfer catalyst in
the presence of hypochlorite as the oxidant.
As part of an ongoing programme on the development of new chiral
control elements for asymmetric synthesis we have recently being study-
ing the use of N-(3,5-di-tert-butyl-4-methoxy)benzylcinchonidinium salts.
These materials were shownto be effective catalytic agents for the asym-
metric phase-transfer Michael addition to chalcone derivatives.[10] Here
we present results regarding the application of these chiral control
elements to the asymmetric epoxidation of a,b-unsaturated ketones.
The new catalysts 3 are derived in two steps from the cinchona
alkaloids and (3,5-di-tert-butyl-4-methoxy)benzyl bromide which is
easily obtained from cheap 2,6-di-tert-butyl-4-methylphenol (BHT). In
order to determine suitable reaction conditions for the catalytic asym-
metric epoxidationof chalcones 1, we initially investigated the reaction
system using 10 mol% of catalyst, with chalcone 1a and sodium hypo-
chlorite as the oxidant (Sch. 1) (Table 1).

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Chiral Quaternary Ammonium Salts
437
Scheme 1.
Table 1. Optimizationof asymmetric epoxidationof chalcone 1a under phase-
transfer condition.
Entry Catalyst Oxidant
Solvent Temp. (ꢀC) Yields (%) eea (%)
1
2
3
4
5
6
7
8
3a
3b
3c
3b
3b
3b
3b
3b
NaOCl
NaOCl
NaOCl
H2O2/KOH Toluene
H2O2/LiOH Toluene
NaOCl
NaOCl
NaOCl
Toluene
Toluene
Toluene
20
20
20
20
20
20
20
0
75
91
83
68
65
68
89
72
50
60
19
15
8
15
38
53
CHCl3
CH2Cl2
Toluene
aEnantiopurity of 2a was determined by HPLC analysis with a Chiralcel OD
column, 2-propanol–hexane (1:9), 1 mL/min, ꢀmax ¼ 254 nm, retention times
major 24.7 min, minor 26.6 min. It was established by analysis of racemic 2a
that the enantiomers were fully resolved.
Chalcone 1a reacted with sodium hypochlorite as the oxidant in the
presence of catalyst 3b (10 mol%), at room temperature, to afford the
epoxide 2a in 91% yield and 60% ee (Table 1, Entry 2). The absolute
configuration of the major enantiomer of 2a was determined from the
optical rotation and chiral HPLC analysis.[9] Catalyst 3b was more
effective thanthe other catalysts (Table 1, Entries 1–3). Inthe case of

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438
Kim et al.
hydrogenperoxide as the oxidant, the reactiondid not proceed at room
temperature in the absence of base. In the presence of KOH as the base,
2a was obtained in 68% yield and low enantioselectivity (Entry 4). The
enantioselectivity was low, when chloroform and methylene chloride were
used as the solvent (Entries 6–7). The stirring rate does not appear to
influence the enantioselectivity of this reaction, however, it does affect
the rate of reactionand substantially decreased reactiontimes canbe
achieved with high stirring rate.
Under the optimized reaction conditions described above (10 mol%
of catalyst 3b, NaOCl, toluene, r.t.), we investigated the catalytic asym-
metric of chalcone derivatives 1. The reactionproceeded smoothly to
afford the corresponding adducts 2 with good enantioselectivities.
Reactionof chalcone derivatives
1, NaOCl as the oxidant, and cin-
chonidinium salt 3b (10 mol%) intoluene at room temperature with
stirring for 48 h afforded the epoxides 2 with good yields and moderate
enantioselectivities (56–78% ee) (Sch. 2) (Table 2). In all cases the
enantiomeric excesses were determined by HPLC analysis.
Scheme 2.
Table 2. Catalytic asymmetric epoxidationof chalcones
with phase-transfer catalyst 3b.
1
Ar1
Ar2
Yields (%)
eea (%)
Ph
Ph
Ph
Ph
Ph
2-Thienyl
p-Me, Ph
2a, 91
2b, 88
2c, 80
2d, 76
2e, 81
2f, 59
60
71
56
78
56
59
p-Cl, Ph
2-Naphthyl
1-Naphthyl
Ph
Ph
aEnantiopurity of 2 was determined by HPLC analysis with a
chiral column(Chiralcel OD for 2a, OD-H for 2e and 2f, an d OJ
for 2b, 2c, an d2d), 2-propanol–hexane (1:9), 1 mL/min,
ꢀmax ¼ 254 nm. In each case, it was established by analysis
of racemic 2 that the enantiomers were fully resolved.

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Chiral Quaternary Ammonium Salts
439
In conclusion, we have developed a new class of asymmetric
phase-transfer catalysts, which show moderate enantioselectivity in the
epoxidation of chalcones. We are currently involved in the further devel-
opment of these catalyst systems and are investigating their applicability
to other asymmetric phase-transfer processes.
EXPERIMENTAL
General
1H NMR spectra were recorded onBruker AC 300 and AC 200F
spectrometers. 13C NMR spectra were recorded at 50 MHz ona Bruker
AC 200F spectrometer. Optical rotations were measured with a JASCO-
DIP-1000 digital polarimeter. Melting points were determined using an
electrothermal apparatus and are uncorrected. Mass spectra were
recorded on Shimadzu QP 5050A and Jeol HX 100/110 instruments.
Chiral HPLC analyses were carried out using Daicel Chiralcel OD,
OD-H, and OJ columns (250 mm, 4.6 mm, eluent: hexane/2-propanol).
N-(4-Methoxy-3,5-di-tert-butylbenzyl)cinchonidinium bromide (3a): To
a suspension of cinchonidine (2.94 g, 10 mmol) in toluene (70 mL) was
added 3,5-di-tert-butyl-4-methoxybenzyl bromide (4.38 g, 14 mmol), and
the mixture was stirred at reflux for 4 h. The reactionmixture was cooled
at room temperature, evaporated, and the residue was recrystallized
from diethyl ether/CH2Cl2 to give the product as a dark brownsolid.
Purificationof the residue by flash chromatography (93:7, dichloro-
methane:methanol) afforded the desired product 3a (91%, 5.57 g) as a
brownsolid: ½ꢁŠ2D5: À77.8 (c ¼ 2, CHCl3); m.p. 210–212ꢀC; IR (film,
cmÀ1) 3504, 3040, 3000, 2950, 1700, 1585, 1500, 1460, 1450, 1410, 1389,
1
1352, 1262, 1225, 1210, 1115, 1010; H NMR (CDCl3, 300 MHz) ꢂ 1.38
(s, 18H), 1.69 (m, 1H), 2.05 (s, 1H), 2.14–2.20 (m, 2H), 2.66 (m, 1H), 3.30
(m, 1H), 3.45 (m, 1H), 3.64 (d, J ¼ 11.4 Hz, 1H), 3.68 (s, 3H), 3.79
(t, J ¼ 8.5 Hz, 1H), 4.86 (t, J ¼ 11.0 Hz, 1H), 5.01 (d, J ¼ 10.3 Hz, 1H),
5.08 (s, 1H), 5.13 (d, J ¼ 5.9 Hz, 1H), 5.50–5.62 (m, 1H), 5.74 (d,
J ¼ 11.0 Hz, 1H), 6.56 (d, J ¼ 6.5 Hz, 1H), 6.74 (d, J ¼ 6.2 Hz, 1H),
7.58–7.61 (m, 2H), 7.69 (s, 2H), 7.74 (d, J ¼ 4.4 Hz, 1H), 8.01–8.07
(m, 2H), 8.85 (d, J ¼ 4.4 Hz, 1H); 13C NMR (CDCl3, 50 MHz) ꢂ 21.54,
24.85, 26.68, 32.01, 35.98, 37.88, 51.33, 60.37, 61.12, 63.59, 64.14, 64.33,
68.53, 117.87, 120.14, 121.06, 122.78, 124.70, 127.61, 129.15, 130.42,
132.37, 136.47, 144.84, 144.95, 148.02, 150.08, 161.19; MS (EI) m/z 527,

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440
Kim et al.
472, 456, 210, 165; HRMS: calcd for C35H46N2Oþ2 526.3559, found
526.3563.
O-Benzyl-N-(4-methoxy-3,5-di-tert-butylbenzyl)cinchonidinium bromide
(3b): To a suspension of N-(3,5-di-tert-butyl-4-methoxybenzyl)cinchonidi-
nium bromide 3a (3.03 g, 5.0 mmol) in40 mL of CH 2Cl2 was added benzyl
bromide (1.29 g, 7.5 mmol) and 2.8 mL of 50% of aqueous KOH
(25.0 mmol). The resulting mixture was stirred for 5 h. The mixture was
diluted with 40 mL of water and extracted with CH2Cl2 (3 ꢁ 40 mL). The
combined organic extracts were dried over MgSO4, filtered and concen-
trated invacuo. The residue was purified by chromatography onsilica gel
(93:7, dichloromethane:methanol) to give product 3b (89%, 3.11 g) as a
yellow solid: ½ꢁŠ2D5: À78.7 (c ¼ 2, CHCl3); m.p. 190–192ꢀC; IR (film,
cmÀ1) 3406, 3060, 2952, 1625, 1615, 1597, 1541, 1537, 1450, 1410, 1388,
1
1351, 1260, 1225, 1210, 1114, 1060, 1010; H NMR (CDCl3, 300 MHz) ꢂ
1.43 (s, 18H), 1.64–1.74 (m, 2H), 2.02–2.09 (m, 1H), 2.30 (m, 1H), 2.55 (s,
1H), 3.09 (t, J ¼ 11.1, 2H), 3.70 (s, 3H), 4.10 (d, J ¼ 7.0, 1H), 4.21 (m, 1H),
4.58–4.74 (m, 3H), 4.98 (d, J ¼ 10.2, 2H), 5.27 (d, J ¼ 17.1, 1H), 5.74 (m,
1H), 5.86 (m, 1H), 6.52 (d, J ¼ 7.6, 1H), 6.65 (s, 1H), 7.33–7.48 (m, 8H),
8.08 (t, J ¼ 8.1, 1H), 8.25 (m, 1H), 8.39 (d, J ¼ 8.9, 1H), 8.64 (s, 1H), 9.29
(d, J ¼ 8.5, 1H); 13C NMR (CDCl3, 50 MHz) ꢂ 22.40, 25.01, 26.98, 32.11,
36.00, 37.80, 50.82, 59.23, 61.42, 64.32, 65.23, 70.01, 72.62, 111.74, 118.74,
127.66, 129.16, 129.72, 130.60, 132.46, 134.06, 135.53, 136.03, 136.54,
137.68, 139.34, 147.71, 152.27, 153.07; MS (EI) m/z 617, 552, 355, 268,
207, 136; HRMS: calcd for C42H53N2Oþ2 617.4107, found 617.4112.
O-Allyl-N-(4-methoxy-3,5-di-tert-butylbenzyl)cinchonidinium bromide
(3c): ½ꢁŠ2D5: À142.5 (c ¼ 2, CHCl3); m.p. 220–221ꢀC; IR (film, cmÀ1
)
3407, 3000, 2949, 1704, 1625, 1596, 1567, 1510, 1502, 1491, 1470, 1454,
1400, 1350, 1210, 1115, 1070, 1010; 1H NMR (CDCl3, 300 MHz) ꢂ
1.47–1.50 (s, 19H), 2.09–2.17 (m, 3H), 2.63 (s, 1H), 3.34–3.47 (m, 3H),
3.75 (s, 3H), 4.01 (m, 1H), 4.28 (m, 2H), 4.64 (d, J ¼ 11.5 Hz, 2H), 5.01 (d,
J ¼ 8.4 Hz, 1H), 5.05 (d, J ¼ 10.5 Hz, 1H), 5.32–5.43 (m, 3H), 5.77 (m,
1H), 6.18 (m, 1H), 6.23 (s, 1H), 6.31 (d, J ¼ 11.5 Hz, 1H), 7.70 (s, 3H),
7.80 (t, J ¼ 7.4 Hz, 1H), 7.93 (m, 1H), 8.14 (d, J ¼ 8.39 Hz, 1H), 8.71 (d,
J ¼ 8.48 Hz, 1H), 8.97 (d, J ¼ 4.39 Hz, 1H); 13C NMR (CDCl3, 50 MHz) ꢂ
20.99, 22.54, 25.28, 27.02, 31.99, 35.92, 37.77, 42.30, 51.04, 59.39, 60.31,
62.72, 64.34, 65.73, 70.30, 115.55, 118.40, 119.17, 120.04, 121.14, 124.40,
125.10, 129.10, 129.85, 130.28, 132.37, 132.47, 136.29, 139.88, 144.82,
148.40, 149.40, 161.18; MS (EI) m/z 567, 470, 394, 268, 167; HRMS:
calcd for C38H50N2Oþ2 566.3872, found 566.3869.
General procedure for epoxidation of chalcones: A mixture of trans-
chalcone (0.3 mmol), 11% aqueous NaOCl (0.35 mL, 0.6 mmol), and

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Chiral Quaternary Ammonium Salts
441
chiral cinchonidinium salt 3b (20.9 mg, 0.03 mmol) in toluene (2 mL)
was stirred at room temperature for 48 h. The mixture was diluted with
water (10 mL) and extracted with ethyl acetate (2 ꢁ 10 mL). The com-
bined organic layers were dried over MgSO4, filtered, concentrated,
and purified by flash chromatography (silica gel, ethyl acet-
ate:hexane ¼ 1:8) to afford the epoxide.
trans-2,3-Epoxy-1,3-diphenylpropan-1-one (2a): Rf 0.51 (EtOAc:
hexane ¼ 1:8); ½ꢁŠ2D5: þ99 (c ¼ 1.3, CHCl3), IR (neat) 1682 (C¼O) cmÀ1
;
1H NMR (CDCl3, 200 MHz) ꢂ 4.08 (d, J ¼ 1.7, 1H), 4.30 (d, J ¼ 1.7,
1H), 7.67–7.28 (m, 8H), 8.01 (d, J ¼ 7.6, 2H); 13C NMR (CDCl3,
50 MHz) ꢂ 59.3, 60.9, 125.7, 129.0–128.2, 133.9, 135.4, 193.1; MS (70 eV)
m/z 224 (M þ 31%), 207, 165, 105 (100), 77, C15H12O2; HPLC (90:10,
hexane:iso-PrOH, 254 nm, 1 mL/min) chiralcel OD column, tR ¼ 24.7 min
(major), tR ¼ 26.6 min(minor).
trans-2,3-Epoxy-3-(4-chlorophenyl)-1-phenylpropan-1-one (2b): Rf
0.48 (EtOAc:hexane ¼ 1:8); ½ꢁŠ2D5: þ15 (c ¼ 3.3, CHCl3), IR (neat) 1680
(C¼O) cmÀ1; 1H NMR (CDCl3, 200 MHz) ꢂ 4.06 (d, J ¼ 1.8, 1H), 4.25 (d,
J ¼ 1.8, 1H), 7.28–7.63 (m, 7H), 8.01 (d, J ¼ 8.1, 2H); 13C NMR (CDCl3,
50 MHz) ꢂ 58.7, 60.9, 127.0, 128.3, 129.0, 134.0, 135.4, 192.7; MS (70 eV)
m/z 258 (M þ 36%), 242, 165, 105 (100), 89, 77, C15H11ClO2; HPLC
(90:10, hexane : iso-PrOH, 254 nm, 1 mL/min) chiralcel OJ column,
tR ¼ 14.5 min(major), tR ¼ 19.6 min(minor).
trans-2,3-Epoxy-3-(naphth-2-yl)-1-phenylpropan-1-one (2c): Rf 0.52
(EtOAc:hexane ¼ 1:8); ½ꢁŠD25: À32 (c ¼ 1, CHCl3), IR (neat) 1670
1
(C¼O) cmÀ1; H NMR (CDCl3, 200 MHz) ꢂ 4.26 (d, J ¼ 1.6, 1H), 4.40
(d, J ¼ 1.6, 1H), 7.50–7.63 (m, 8H), 7.84–7.92 (m, 3H), 8.03 (d, J ¼ 8.0,
1H); 13C NMR (CDCl3, 50 MHz) ꢂ 59.2, 61.0, 122.3, 125.7, 126.7,
127.8–128.7, 133.9, 192.9; MS (70 eV) m/z 274 (M þ 0.8%), 207, 167,
149 (100), 105, 71, C19H14O2; HPLC (90:10, hexane:iso-PrOH, 254 nm,
1 mL/min) chiralcel OJ column, tR ¼ 20.5 min(major), tR ¼ 27.2 min
(minor).
trans-2,3-Epoxy-3-(naphth-1-yl)-1-phenylpropan-1-one (2d): Rf 0.53
(EtOAc:hexane ¼ 1:8); ½ꢁŠD25: À67 (c ¼ 2, CHCl3), IR (neat) 1672
1
(C¼O) cmÀ1; H NMR (CDCl3, 200 MHz) ꢂ 4.25 (d, J ¼ 1.5, 1H), 4.73
(d, J ¼ 1.5, 1H), 7.49–7.64 (m, 7H), 7.85–8.10 (m, 5H); 13C NMR (CDCl3,
50 MHz) ꢂ 57.8, 59.6, 122.4, 125.8, 126.3, 126.7, 128.3, 128.9, 133.3,
193.2; MS (70 eV) m/z 274 (M þ 36%), 207, 167, 149 (100), 105, 71,
C19H14O2; HPLC (90:10, hexane:iso-PrOH, 254 nm, 1 mL/min) chiralcel
OJ column, tR ¼ 15.5 min(major), tR ¼ 19.6 min(minor).
trans-2,3-Epoxy-3-phenyl-1-(thien-2-yl)propan-1-one (2e): Rf 0.5
(EtOAc:hexane ¼ 1:8); ½ꢁŠD25: þ91 (c ¼ 2.4, CHCl3), IR (neat) 1700

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Kim et al.
1
(C¼O) cmÀ1; H NMR (CDCl3, 200 MHz) ꢂ 4.07 (d, J ¼ 1.5, 1H), 4.17
(d, J ¼ 1.5, 1H), 7.17 (dd, J ¼ 3.7, 1H), 7.27–7.42 (m, 5H), 7.74 (d,
J ¼ 3.7, 1H), 7.99 (d, J ¼ 3.4, 1H); 13C NMR (CDCl3, 50 MHz) ꢂ 59.3,
61.9, 125.7, 128.2, 128.4, 128.8, 133.5, 135.1, 193.9; MS (70 eV) m/z 230
(M þ 35%), 213, 173, 111 (100), 96, 89, 77, C13H10O2S; HPLC (80:20,
hexane:iso-PrOH, 254 nm, 1 mL/min) chiralcel OD-H column, tR ¼
19.6 min(minor), tR ¼ 20.8 min(major).
trans-2,3-Epoxy-3-phenyl-1-(4-methylphenyl)propan-1-one (2f ): Rf
0.48 (EtOAc:hexane ¼ 1:8); ½ꢁŠ2D5: þ298 (c ¼ 2, CHCl3), IR (neat)
1
1670(C¼O) cmÀ1; H NMR (CDCl3, 200 MHz) ꢂ 2.42 (s, 3H), 4.07 (d,
J ¼ 1.5, 1H), 4.28 (d, J ¼ 1.5, 1H), 7.33 (d, J ¼ 7.8, 2H), 7.39 (s, 5H), 7.92
(d, J ¼ 7.8, 2H); 13C NMR (CDCl3, 50 MHz) ꢂ 59.2, 60.9, 125.7, 128.4,
128.6, 128.9, 135.6, 145.0, 192.0; MS(70 eV) m/z 238 (M þ 25%), 221,
165, 119 (100), 91, 77, C16H14O2; HPLC (80:20, hexane:iso-PrOH,
254 nm, 0.5 mL/min) chiralcel OD-H column, tR ¼ 24.8 min(major),
tR ¼ 25.8 min(minor).
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1. (a) Lohray, B.B. Synthesis 1992, 1035; (b) Katsukis, T. J. Synth. Org.
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Chiral Quaternary Ammonium Salts
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Received inJapanOctober 22, 2001

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