Water-soluble calixarenes as new inverse phase-transfer catalysts. Their application to aldol-type condensation and Michael addition reactions in water

Article abstract of DOI:10.1016/S0040-4020(01)00572-5

Aldol-type condensation and Michael addition reactions of activated methyl and methylene compounds in aqueous NaOH solution have been developed without the need for any added organic solvents. The water-soluble calix[n]arenes, which contain trimethylammon

Full text of DOI:10.1016/S0040-4020(01)00572-5

TETRAHEDRON
Pergamon
Tetrahedron 57 (2001) 6169±6173
Water-soluble calixarenes as new inverse phase-transfer catalysts.
Their application to aldol-type condensation and Michael addition
reactions in water
²
Shoichi Shimizu,p Seiji Shirakawa, Takashi Suzuki and Yasuyuki Sasaki
Department of Applied Molecular Chemistry and High Technology Research Center, College of Industrial Technology, Nihon University,
Narashino, Chiba 275-8575, Japan
Received 17 April 2001; accepted 21 May 2001
AbstractÐAldol-type condensation and Michael addition reactions of activated methyl and methylene compounds in aqueous NaOH
solution have been developed without the need for any added organic solvents. The water-soluble calix[n]arenes, which contain trimethyl-
ammoniomethyl groups on the upper rim, were used as inverse phase-transfer catalysts, resulting in the corresponding products in good to
excellent yields. q 2001 Elsevier Science Ltd. All rights reserved.
1. Introduction
smoothly in an aqueous environment to afford the desired
products,10 as do the alkylation reactions of active methyl-
ene compounds with alkyl halides in aqueous NaOH solu-
tion (Scheme 1).11 We have also reported that metal
complexes with water-soluble calix[4]arenes which contain
two phosphine moieties on the upper rim are able to func-
tion, not only as homogeneous metal catalysts, but also as
inverse phase-transfer catalysts in aqueous biphasic hydro-
formylation reactions.12,13 We describe herein that the
water-soluble calix[n]arenes as the inverse phase-transfer
catalysts can be applied to aldol-type condensation and
Michael addition reactions in aqueous NaOH solution. In
these reactions, only the desired compound is formed as a
product and the catalyst in the aqueous phase can be
recycled after the separation of organic products.
The use of water as a medium for organic reactions has a
number of potential advantages: (i) it is the cheapest solvent
available on earth; (ii) it is non-hazardous to the environ-
ment and non-toxic; (iii) isolation of the organic products
can be performed by simple phase separation.1 There are
bene®cial effects of aqueous solvents on rates and selec-
tivities of important organic transformations, e.g. Diels±
Alder reactions, aldol reactions and Michael additions.1,2
In some cases, polar water-miscible organic solvents (co-
solvents)3 or surfactants4±6 are used when the solubility of
substrate in water is not suf®ciently high, but their use
usually complicates workup procedures particularly in
regard to catalyst recovery.7 The use of inverse phase-
transfer catalysts has the potential to solve this dilemma,8
since they would facilitate reactions between two immisci-
ble reactants via the transport of an organic substrate into an
aqueous solution of a second reactant in which reactions
would take place. One advantage of water-soluble catalysts
is that they can be reused after simple decantation or
extraction of the water-insoluble products.
2. Results and discussion
The activity and selectivity of the water-soluble calix[n]-
arenes 1n was ®rst tested for the case of aldol-type conden-
sation reactions of indene and acetophenone with aromatic
We recently discovered that, by using water-soluble calix-
[n]arenes,9 p-(trimethylammoniomethyl)calix[n]arene methyl
ethers 1n (nˆ4, 6 and 8), as inverse phase-transfer catalysts,
nucleophilic substitution reactions of alkyl halides with
simple nucleophiles such as sodium cyanide proceed
Keywords: calixarenes; catalysis; water; aldol reactions.
Corresponding author. Tel.: 181-47-474-2568; fax: 181-47-474-2579;
p
e-mail: s5simizu@cit.nihon-u.ac.jp
Present address: Department of Chemistry, Graduate School of Science,
Kyoto University, Sakyo, Kyoto 606-8502, Japan.
Scheme 1. R1ˆC6H5, CH3CO, C6H5CO, 2-ClC6H4, 1-C10H7; R2ˆCH3CO,
CN; RˆC8H17, 4-t-BuC6H4CH2, Cl(CH2)4, 1-C10H7CH2; XˆBr, l.
²
0040±4020/01/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(01)00572-5

6170
S. Shimizu et al. / Tetrahedron 57 (2001) 6169±6173
Table 1. Aldol-type condensations in aqueous NaOH solution
Entry
3
Catalyst
Time (h)
4
Yield (%)
1
2
3
4
None
b-CDa
CTABb
14
1.5
1.5
1.5
1.5
0
0
82
90
5
6
7
8
None
b-CDa
CTABb
14
0.5
0.5
0.5
0.5
25
53
83
92
a
b-Cyclodextrin.
Cetyltrimethylammonium bromide 10 mol%.
b
aldehydes in aqueous NaOH solutions, and the results are
summarized in Table 1. The treatment of indene 3a with
benzaldehyde 2a in 5N aqueous NaOH solution for 1.5 h at
room temperature resulted in no reaction product being
produced (entry 1). No acceleration effect was observed
when b-cyclodextrin as an inverse phase-transfer catalyst
was added to the reaction mixture (entry 2). In contrast, the
addition of the water-soluble calix[n]arenes 1n resulted in
an excellent yield of aldol-type condensation product, E-1-
benzylidene-1H-indene 4a (entry 4). Neither products
derived from non-dehydration nor bis-condensation was
formed. For the sake of comparison, the same reaction
was also conducted in aqueous micelles using the well-
known cationic surfactant,5,6,14 cetyltrimethylammonium
bromide (CTAB) (entry 3). Although the micellar reaction
gave a similar selectivity and product yield,6 the catalyst 14
was superior to CTAB in terms of product separation and
catalyst recovery. The workup procedure for the reaction
using 14 was extremely simple, compared with that of
CTAB, because the distribution of 1n into the organic
phase was negligible10 and no emulsion was observed
during the reaction and workup. The aldol condensation of
acetophenone 3b with 2a also proceeded ef®ciently in
the presence of 14 to afford the a,b-unsaturated ketone 4b
(entry 8).
Table 2. Aldol-type condensations of phenylacetonitrile with various
aromatic aldehydes in aqueous NaOH solution
Entry
2
Catalyst 5a/2 Time (h) Yield (%)
6
7a
Some examples of the reaction of phenylacetonitrile with
aromatic aldehydes in aqueous NaOH solution are shown in
Table 2. In all cases, along with aldol-type condensation, a
Michael addition of phenylacetonitrile to the ®rst conden-
sation product 6 took place to give the a,g-dinitrile
compound 7. The con®guration of products 6a±d is exclu-
sively Z, because the chemical shift of the aromatic protons
in the 1H NMR spectra indicates that the aromatic rings are
coplanar with the double bond.15 However, in the presence
of the catalyst 14 the reactions proceeded with good selec-
tivity. The product selectivity was highly dependent on the
molar ratio of 5a to 2. Thus, the a,b-unsaturated nitrile 6a
was obtained as the major product in the reaction of 5a with
2a at a lower molar ratio (entry 8), while a,g-dinitrile 7a
was obtained at a higher molar ratio (entry 2). Similarly,
good to high selectivity was observed for 4-chlorobenzalde-
hyde 2b (entries 10 and 12), and 1-naphthaldehyde 2d
(entry 17).
1
2
3
4
None
14
None
14
5.0
5.0
2.0
2.0
1.1
0.5
0.5
0.5
1.0
1.0
0.5
0.5
0.5
2.0
2.0
2.0
36 38
5
14
23 67
76 10
62 Trace
76
91
90
0
5
14
6b
7b
8b
None
CTABc
14
3
3
9
None
14
None
14
5.0
5.0
1.1
1.1
2.0
2.0
1.0
1.0
53
3
4
94
10
11
12
48 Trace
84 12
13
14
15
14
None
14
5.0
1.1
1.1
2.0
1.0
1.0
11 87
19 Trace
47 16
16
17
None
14
1.1
1.1
1.0
1.0
35 Trace
87 Trace
Encouraged by the above observations, we also examined
the Michael addition reactions of activated methyl and
methylene compounds to a,b-unsaturated ketones and
nitriles in aqueous NaOH solution. The results are summa-
rized in Table 3. With the exception of acetophenone, the
a
The a,g-nitriles 7a±c were isolated as a mixture of syn/syn, syn/anti, and
anti/anti diastereomers. The ratios were determined by 1H NMR.
An 8 mmol amount of 2a was used, and yields were based on 4.0 mmol
amount of 5a.
b
c
Cetyltrimethylammonium bromide 10 mol%.

S. Shimizu et al. / Tetrahedron 57 (2001) 6169±6173
6171
Table 3. Michael additions of activated methyl and methylene compounds to a,b-unsaturated ketones and nitrile in aqueous NaOH solution
Entry
Donor
(8 mmol)
Acceptor
(4 mmol)
Catalyst
(1 mol%)
Conditionsa
(8C, h)
Product
Yieldb
(%)
a
b
c
An aqueous 5N NaOH solution (3 mL) was used.
The Michael adducts 9a±e were isolated as a mixture of syn and anti diastereomers. The ratios were determined by 1H NMR.
Aqueous layer used in entry 3.
reactions proceeded ef®ciently in the presence of a catalytic
amount (1 mol%) of 1n to afford the corresponding Michael
adducts. For instance, in the reaction of phenylacetonitrile
5a with cinnamonitrile 8a the yield of Michael adduct 9a
was increased from 19% to 79% by the addition of 16 (entry
3). Unfortunately, however, the catalytic activity was
reduced to approximately 66% with reuse of the aqueous
layer, which contained the catalyst (entry 4). The use of the
catalyst 16 in the reaction of 4-methoxyphenylacetone 5c
and 2-cyclohexen-1-one 8b increased the yield of 9e to
79%, that is, 26 times larger than that observed in its
absence (entries 13 and 14). Treatment of 3b with 4b at
608C for 10 h afforded the 1,4-adduct 9f in 35% yield
(entry 16). This result suggests that a one-pot synthesis of
9f from 3b and 2a can be achieved by controlling the molar
ratios of reactants and the reaction temperature. Indeed, the
reaction of 3b with 2a at room temperature gave 4b in an
excellent yield (entry 8 in Table 1). In the reaction of
1-naphthylacetonitrile 5b with 8b, the activities of the
catalysts 1 increase in the order of 14#16,18 (entries
10±12).10,11 This result may be a re¯ection of the following
interfacial mechanism.11 In the aqueous phase near the inter-
face, the water-soluble calix[n]arenes 1n would be expected
to form host-guest complexes with the carbanion which
arises via the deprotonation of Michael donor with hydrox-
ide ions, and the nucleophilic attack of the anion on the
Michael acceptor would take place at the interface. This is
somewhat different from the Makosza interfacial mecha-
nism of normal phase-transfer catalysis, which involves
C±C bond-forming reaction within balk organic phase as
a ®nal step.16 The size of the cavity of 18 may be suf®ciently
large to accommodate the naphthyl ring, but those of 14 and
16 may be somewhat small. Thus, the ef®ciency of the
catalyst 1n varies depending on the size of the Michael
donor molecules, but not the Michael acceptor molecules.
Aldol-type condensation reactions using catalysts 1n also
most likely proceed via this mechanism.
In conclusion, water-soluble calix[n]arene derivatives 1n
were found to catalyze aldol-type condensation and Michael
addition reactions of activated methyl and methylene
compounds smoothly in aqueous NaOH solution. This
water-soluble catalytic system employing 1n provides
powerful options in aqueous biphasic reactions for synthetic
chemistry and process engineering.
3. Experimental
3.1. General
1H and 13C NMR spectra were recorded on a Bruker
Avance-400s spectrometer at 400 and 100 MHz, respec-
tively, in CDCl3 with tetramethylsilane as an internal
standard and J values are given in Hz. The MS spectra
were measured on a JEOL JMS-AX500 mass spectrometer

6172
S. Shimizu et al. / Tetrahedron 57 (2001) 6169±6173
(EI, 70 eV) using GC±MS coupling. IR spectra were
recorded on a Bio-Rad FTS-60A spectrometer. Preparative
gel-permeation chromatography (GPC) was done with a JAI
model 908 liquid chromatograph with a couple of JAIGEL-
1H and 2H columns.
3.3.5. b-(4-Methoxyphenyl)-a-pheylacrylonitrile (6c).15a
1H NMR (400 MHz, CDCl3) d 7.90±7.87 (m, 2H), 7.66±
7.64 (m, 2H), 7.46±7.36 (m, 4H), 6.99±6.96 (m, 2H), 3.86
(s, 3H); 13C NMR (100 MHz, CDCl3) d 161.39, 141.85,
134.80, 131.18, 128.98, 128.72, 126.48, 125.74, 118.54,
114.36, 108.58, 55.40; IR (KBr) 3016, 2844, 2210, 1603,
1595, 1512, 1255, 1180, 1027, 832, 694 cm21; MS (EI) m/z
235 (M1, 100), 204 (8), 190 (10), 165 (16).
3.2. Materials
The water-soluble calix[n]arenes 1n´nH2O (nˆ4, 6 and 8)
were prepared by following literature methods17 and identi-
®ed by IR and NMR spectroscopy as well as elemental
analysis. Cetyltrimethylammonium bromide and b-cyclo-
dextrin were purchased from Tokyo Kasei Kogyo, and
used without further puri®cation.
3.3.6. b-Naphthylmethyl-a-pheylacrylonitrile (6d). 1H
NMR (400 MHz, CDCl3) d 8.27 (s, 1H), 8.08 (d, 1H,
Jˆ7.2 Hz), 7.98±7.89 (m, 3H), 7.78±7.76 (m, 2H), 7.59±
7.42 (m, 6H); 13C NMR (100 MHz, CDCl3) d 140.22,
134.40, 133.70, 131.71, 131.27, 130.75, 129.48, 129.20,
129.02, 127.07, 126.99, 126.45, 126.30, 125.57, 123.43,
117.63, 115.57; IR (KBr) 3041, 2219, 1448, 890, 781,
758, 685 cm21; MS (EI) m/z 255 (M1, 100), 254 (66), 240
(18), 228 (15), 177 (13), 127 (12), 113 (13).
3.3. Typical procedure for the aldol-type condensation
and Michael addition
To a 10 mL three-necked ¯ask containing 1n´nH2O
(1 mol%) was added an aqueous 5N NaOH solution
(3 mL). An activated methyl or methylene compound and
aldehyde or enone were then introduced. The reaction
mixture was stirred with a magnetic stirring bar at
800 rpm for 0.2±2 h at rt2608C (depending on the
substrates). After addition of water (5 mL), the resulting
mixture was extracted with chloroform (10 mL£3). The
combined extracts were dried with anhydrous Na2SO4 and
evaporated. The products were puri®ed by preparative GPC
and the isolated yields were determined.
3.3.7. 1,2,3-Triphenyl-1,3-propanedicarbonitrile (7a).
1
(Diastereomer ratio: A/B/Cˆ62/32/6) H NMR (400 MHz,
CDCl3) d 7.36±6.64 (m, 15H), 4.82 (d, 0.32H, Jˆ5.2 Hz,
for B), 4.45 (d, 0.32H, Jˆ10.6 Hz, for B), 4.41 (d, 0.12H,
Jˆ7.7 Hz, for C), 4.13 (d, 1.24H, Jˆ8.1 Hz, for A), 3.86 (t,
0.06H, Jˆ7.7 Hz, for C), 3.45 (dd, 0.32H, Jˆ10.6, 5.2 Hz,
for B), 3.37 (t, 0.62H, Jˆ8.1 Hz, for A); IR (KBr) 3065,
3033, 2245, 1495, 1455, 757, 747, 701 cm21; MS (EI) m/z
322 (M1), 206 (100), 179.
3.3.8.
2-(4-Chlorophenyl)-1,3-diphenyl-1,3-propane-
3.3.1. E-1-Benzylidene-1H-indene (4a).6 1H NMR (400
MHz, CDCl3) d 7.71±6.98 (m, 12H); 13C NMR (100
MHz, CDCl3) d 142.08, 140.09, 137.44, 136.93, 134.56,
130.24, 128.72, 128.69, 128.34, 127.56, 126.11, 125.16,
120.96, 119.15; IR (KBr) 3062, 1443, 795, 762, 694,
505 cm21; MS (EI) m/z 204 (M1, 100), 203 (95), 202
(62), 101 (27), 89 (10), 76 (6).
dicarbonitrile (7b). (Diastereomer ratio: A/B/Cˆ64/27/9)
1H NMR (400 MHz, CDCl3) d 7.38±6.55 (m, 14H), 4.82 (d,
0.27H, Jˆ5.0 Hz, for B), 4.40 (d, 0.27H, Jˆ10.7 Hz, for B),
4.37 (d, 0.18H, Jˆ7.7 Hz, for C), 4.11 (d, 1.28H, Jˆ8.1 Hz,
for A), 3.86 (t, 0.09H, Jˆ7.7 Hz, for C), 3.45 (dd, 0.27H,
Jˆ10.7, 5.0 Hz, for B), 3.37 (t, 0.64H, Jˆ8.1 Hz, for A); IR
(KBr) 3066, 3035, 2244, 1495, 1456, 1095, 1015, 755, 733,
700 cm21; MS (EI) m/z 358 ([M12]1), 356 (M1), 240
(100), 213, 205, 178, 117.
3.3.2. Benylideneacetophenone (4b).5b 1H NMR (400
MHz, CDCl3) d 8.04±7.39 (m, 12H); 13C NMR (100
MHz, CDCl3) d 190.58, 144.86, 138.22, 134.89, 132.79,
130.56, 128.97, 128.64, 128.51, 128.46, 122.10; IR (KBr)
3081, 2917, 1664, 1605, 1576, 1449, 1336, 1215, 1016, 747,
689 cm21; MS (EI) m/z 208 (M1, 100), 207 (97), 179 (16),
131 (41), 105 (21), 103 (22), 77 (58), 51 (16).
3.3.9.
2-(4-Methoxyphenyl)-1,3-diphenyl-1,3-propane-
dicarbonitrile (7c). (Diastereomer ratio: A/B/Cˆ64/28/8)
1H NMR (400 MHz, CDCl3) d 7.37±6.53 (m, 14H), 4.78 (d,
0.28H, Jˆ5.1 Hz, for B), 4.39 (d, 0.28H, Jˆ10.5 Hz, for B),
4.36 (d, 0.16H, Jˆ7.7 Hz, for C), 4.09 (d, 1.28H, Jˆ8.0 Hz,
for A), 3.85±3.81 (t, 0.08H, for C), 3.78 (s, 1.92H, for A), 3.70
(s, 0.24H, for C), 3.69 (s, 0.84H, for B), 3.41 (dd, 0.28H,
Jˆ10.5, 5.1 Hz, for B), 3.33 (t, 0.64H, Jˆ8.0 Hz, for A); IR
(KBr) 3002, 2965, 2839, 2241, 1516, 1455, 1254, 1181, 1032,
760, 743, 699 cm21; MS (EI) m/z 352 (M1), 236 (100).
3.3.3. a-Phenylcinnamonitrile (6a).15b 1H NMR (400
MHz, CDCl3) d 7.90±7.88 (m, 2H), 7.69±7.67 (m, 2H),
7.54 (s, 1H), 7.50±7.38 (m, 6H); 13C NMR (100 MHz,
CDCl3) d 142.24, 134.43, 133.69, 130.52, 129.25, 129.19,
129.05, 128.94, 125.97, 117.99, 111.64; IR (KBr) 3032,
2019, 1447, 938, 908, 761, 744, 692, 518 cm21; MS (EI)
m/z 205 (M1, 100), 204 (71), 190 (31), 177 (16), 102 (10),
89 (19).
3.3.10. 2-(1-Naphthyl)-1,3-diphenyl-1,3-propanedicarbo-
nitrile (7d). This compound has not been isolated because
of its trace amount. MS (EI) m/z 372 (M1), 256, 178 (100).
3.3.4. b-(4-Chlorophenyl)-a-pheylacrylonitrile (6b).15a
1H NMR (400 MHz, CDCl3) d 7.84±7.82 (m, 2H), 7.68±
7.66 (m, 2H), 7.48±7.41 (m, 6H); 13C NMR (100 MHz,
CDCl3) d 140.58, 136.39, 134.09, 132.13, 130.45, 129.41,
129.20, 129.10, 125.96, 117.73, 112.22; IR (KBr) 3057,
3036, 2220, 1589, 1493, 1448, 1092, 829, 762, 691,
522 cm21; MS (EI) m/z 241 ([M12]1, 29), 239 (M1, 89),
204 (100), 177 (20), 101 (13), 88 (26).
3.3.11. 1,2-Diphenyl-1,3-propanedicarbonitrile (9a). (Dia-
stereomer ratio: A/Bˆ60/40) 1H NMR (400 MHz, CDCl3) d
7.37±7.17 (m, 10H), 4.29 (d, 0.6H, Jˆ8.0 Hz, for A), 4.17
(d, 0.4H, Jˆ6.8 Hz, for B), 3.50±3.38 (m, 1H), 2.98 (dd,
0.4H, Jˆ16.8, 9.6 Hz, for B), 2.88±2.78 (m, 1H), 2.98 (dd,
0.6H, Jˆ16.9, 7.3 Hz, for A); IR (KBr) 3065, 3035, 2924,
2245, 1601, 1494, 1456, 1422, 760, 701 cm21; MS (EI) m/z
246 (M1), 130 (100), 117, 103, 77.

S. Shimizu et al. / Tetrahedron 57 (2001) 6169±6173
6173
Society: Washington, DC, 1994; pp. 303±317. (d) Lubineau,
Â
A.; Auge, J.; Queneau, Y. Synthesis 1994, 741±760. (e) Li,
C.-J. Chem. Rev. 1993, 93, 2023±2035.
3.3.12. a-(3-Oxocyclohexyl)phenylacetonitrile (9b). (Dia-
stereomer ratio: A/Bˆ50/50) 1H NMR (400 MHz, CDCl3) d
7.42±7.27 (m, 5H), 3.92 (d, 0.5H, Jˆ4.5 Hz, for A), 3.76 (d,
0.5H, Jˆ5.8 Hz, for B), 2.43±1.59 (m, 9H); IR (KBr) 2945,
2870, 2240, 1712, 1453, 1228, 762, 702 cm21; MS (EI) m/z
213 (M1), 117, 97 (100), 69.
3. (a) Kobayashi, S.; Ishitani, H. J. Chem. Soc., Chem. Commun.
1995, 1379. (b) Kobayashi, S.; Hachiya, I. J. Org. Chem.
1994, 59, 3590±3596. (c) Kobayashi, S.; Hachiya, I.;
Yamanoi, Y. Bull. Chem. Soc. Jpn. 1994, 67, 2342±2342.
(d) Hachiya, I.; Kobayashi, S. J. Org. Chem. 1993, 58,
6958±6960.
3.3.13. 3-Benzoyl-1,2-diphenylpropanecarbonitrile (9c).
(Diastereomer ratio: A/Bˆ50/50) 1H NMR (400 MHz,
CDCl3) d 7.96±7.86 (m, 2H), 7.42±7.07 (m, 13H), 4.50
(d, 0.5H, Jˆ5.3 Hz, for A), 4.22 (d, 0.5H, Jˆ6.0 Hz, for
B), 3.94±3.70 (m, 2H), 3.52 (dd, 0.5H, Jˆ17.9, 5.0 Hz),
3.38 (dd, 0.5H, Jˆ17.4, 4.8 Hz); IR (KBr) 3063, 3032,
2240, 1684, 1452, 1212, 754, 733, 700 cm21; MS (EI) m/z
325 (M1), 209, 205, 105 (100), 77.
4. (a) Manabe, K.; Mori, Y.; Wakabayashi, T.; Nagayama, S.;
Kobayash, S. J. Am. Chem. Soc. 2000, 122, 7202±7207.
(b) Mori, Y.; Kakumoto, K.; Manabe, K.; Kobayashi, S.
Tetrahedron Lett. 2000, 41, 3107±3111. (c) Tian, H.-Y.;
Chen, Y.-J.; Wang, D.; Zeng, C.-C.; Li, C.-J. Tetrahedron
Lett. 2000, 41, 2529±2532. (d) Manabe, K.; Kobayashi, S.
Org. Lett. 1999, 1, 1965±1967. (e) Kobayashi, S.; Waka-
bayashi, T.; Nagayama, S.; Oyamada, H. Tetrahedron Lett.
1997, 38, 4559±4562. (f) Kobayashi, S.; Wakabayashi, T.;
Oyamada, H. Chem. Lett. 1997, 831±832.
3.3.14. a-(3-Oxocyclohexyl)-1-naphtylacetonitrile (9d).
(Diastereomer ratio: A/Bˆ50/50) 1H NMR (400 MHz,
CDCl3) d 7.93±7.49 (m, 7H), 4.75 (d, 0.5H, Jˆ4.0 Hz,
for A), 4.56 (d, 0.5H, Jˆ4.7 Hz, for B), 2.54±1.41 (m,
9H); IR (KBr) 3054, 2946, 2869, 2241, 1713, 1228, 802,
780 cm21; MS (EI) m/z 263 (M1), 167, 97 (100), 69.
5. (a) Ballini, R.; Bosica, G. Tetrahedron Lett. 1996, 37, 8027±
8030. (b) Nivalkar, K. R.; Mudaliar, C. D.; Mashraqui, S. H.
J. Chem. Res. (S) 1992, 98±99. (c) Bassetti, M.; Cerichelli, G.;
Floris, B. Gazz. Chim. Ital. 1991, 121, 527±532.
3.3.15.
1-(3-Oxocyclohexyl)-1-(4-methoxyphenyl)-2-
6. Fringuelli, F.; Pani, G.; Piermatti, O.; Pizzo, F. Tetrahedron
1994, 50, 11499±11508.
propanone (9e). (Diastereomer ratio: A/Bˆ50/50) 1H
NMR (400 MHz, CDCl3) d 7.12±7.05 (m, 2H), 6.89±6.84
(m, 2H), 3.85 (s, 1.5H), 3.80 (s, 1.5H), 3.48 (d, 0.5H, Jˆ
2.6 Hz, for A), 3.46 (d, 0.5H, Jˆ1.8 Hz, for B), 2.66±1.12
(m, 12H); IR (KBr) 2953, 1711, 1511, 1253 cm21; MS (EI)
m/z 260 (M1), 217 (100), 121.
7. Nagayama, S.; Kobayashi, S. Angew. Chem. Int. Ed. 2000, 39,
567±569. Nagayama, S.; Kobayashi, S. Angew. Chem. 2000,
112, 578±581.
8. (a) Goldberg, Y. Phase Transfer Catalysis: Selected Problems
and Applications; Gordon: Berkshire, 1992; pp. 359±366.
(b) Starks, C. M.; Liotta, C. L.; Halpern, M. Phase-Transfer
Catalysis: Fundamentals, Applications, and Industrial
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9. (a) Gutsche, C. D. Calixarenes, Monographs in Supra-
molecular Chemistry; The Royal Society of Chemistry:
Cambridge, 1989. (b) In Calixarenes: A Versatile Class of
1
3.3.16. 1,3,5-Triphenyl-1,5-pentanedione (9f). H NMR
(400 MHz, CDCl3) d 7.95 (d, 4H, Jˆ7.4 Hz), 7.55 (t, 2H,
Jˆ7.1 Hz), 7.44 (t, 4H, Jˆ7.7 Hz), 7.29±7.25 (m, 4H),
7.20±7.16 (m, 1H), 4.09±4.04 (m, 1H), 3.50 (dd, 2H, Jˆ
16.6, 7.0 Hz), 3.36 (dd, 2H, Jˆ16.6, 7.1 Hz); 13C NMR
(100 MHz, CDCl3) d 198.56, 143.98, 137.28, 132.99,
128.65, 128.60, 128.18, 127.55, 126.72, 44.98, 37.46; IR
(KBr) 3063, 3029, 2899, 1695, 1678, 759, 698 cm21; MS
(EI) m/z 328 (M1), 209 (77), 105 (100), 77 (77).
È
Macrocyclic Compounds; Vicens, J., Bohmer, V., Eds.;
Kluwer Academic Publishers: Dordrecht, 1991. (c) Bohmer,
È
È
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V. Angew. Chem. 1995, 107, 785. (d) Gutsche, C. D.
Caixarenes Revisited, Monographs in Supramolecular
Chemistry; The Royal Society of Chemistry: Cambridge,
1998.
Acknowledgements
10. Shimizu, S.; Kito, K.; Sasaki, Y.; Hirai, C. Chem. Commun.
1997, 1629±1630.
This work was supported, in part, by Nihon University.
11. Shimizu, S.; Suzuki, T.; Sasaki, Y.; Hirai, C. Synlett 2000,
1664±1666.
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