Novel sucrose-based macrocyclic receptors for enantioselective recognition of chiral ammonium cations

Article abstract of DOI:10.1016/j.tetasy.2012.10.003

A new synthetic route to macrocyclic sucrose-based receptors with different substituents at the ring nitrogen atom is described. Very good enantioselectivity toward phenylethylammonium chloride was observed [a much stronger complex with the cation of the (S)-amine was formed] although the K_a values were low. Much higher K_a (1.4 × 10 ⁴ M^-1 in CDCl₃/CD₃OD) values of the complexes with aminoacid derivatives (especially valine) were found although this time the enantioselectivities were moderate.

Full text of DOI:10.1016/j.tetasy.2012.10.003

Tetrahedron: Asymmetry 23 (2012) 1474–1479
Contents lists available at SciVerse ScienceDirect
Tetrahedron: Asymmetry
journal homepage: www.elsevier.com/locate/tetasy
Novel sucrose-based macrocyclic receptors for enantioselective recognition
of chiral ammonium cations
⇑
Mykhaylo A. Potopnyk, Bartosz Lewandowski, Sławomir Jarosz
Institute of Organic Chemistry, Polish Academy of Sciences, 01-224 Kasprzaka 44/52, Warsaw, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 31 July 2012
Accepted 8 October 2012
A new synthetic route to macrocyclic sucrose-based receptors with different substituents at the ring
nitrogen atom is described. Very good enantioselectivity toward phenylethylammonium chloride was
observed [a much stronger complex with the cation of the (S)-amine was formed] although the Ka values
were low. Much higher Ka (1.4 ꢀ 104 Mꢁ1 in CDCl3/CD3OD) values of the complexes with aminoacid
derivatives (especially valine) were found although this time the enantioselectivities were moderate.
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
OH
HO
OH
HO
6'
6'
6
BnO
The synthesis of macrocyclic receptors which are able to recog-
nize chiral ammonium cations with high enantioselectivity is of
considerable importance.1 The design of these receptors is based
on common enantiomerically pure starting platforms such as ami-
no acids,2 binaphthyl,3 salen,3b terpenes,4 or sugars.5 The latter in
particular represent a unique possibility for the preparation of var-
ious stereochemically different molecules. The monosaccharide
platform is usually applied for the construction of such macrocy-
cles;5a much less common are receptors based on disaccharide
scaffolds.5 This unique disaccharide platform is represented by su-
crose, an inexpensive raw material available in 160 million tons
per year.6 Sucrose, in addition to its application in the food indus-
try, is also of interest in many chemical and biochemical laborato-
ries for the preparation of fine chemicals, biodegradable polymers,
and surfactants.7
6
O
O
1'
BnO
Fruc
Glu
Glu
Fruc
O
OBn
X
BnO
OBn
OBn
1
X
Y
Glu
Fruc
2a
2b
2c
X = Y = O;
X = O, Y = NBn;
X = Y = NBn
N
N
We have elaborated on a convenient route to 10,2,3,30,4,40-hexa-
O-benzylsucrose 1,8 the starting material used for the preparation
of cyclic analogs with a C1 (e.g. 2a-c)9 or C2-symmetry (e.g. 3)
(Fig. 1).10 Especially interesting were compounds of type 2. Deriva-
tive 2b containing one protected nitrogen atom was able to complex
only achiral cations (e.g. Na+, K+),9a while 2c with three protected
Glu
Fruc
Fruc
N
H
H
O
O
N
N
6
6
6'
N
6'
N
N
nitrogens9b was found to complex
enantioselectivity.11
a-phenylethylamine with good
Glu
N
In compounds 2b and 2c, the nitrogen atom(s) is permanently
blocked; removal of the benzyl protecting group from the ring
nitrogen atom is not possible without deprotection of the sucrose
skeleton. Herein we report an approach to the macrocycle with
the ‘free’ nitrogen atom, which might allow us to introduce
3
Figure 1. Sucrose-derived macrocycles.
additional substituents with different electronic properties. Such
modified macrocycles might have better complexing abilities;
moreover, it should be possible to tune this ability by changing
the character of the blocks placed on the nitrogen atom.
⇑
Corresponding author. Tel.: +48 22 343 23 20; fax: +48 22 632 66 81.
E-mail address: slawomir.jarosz@icho.edu.pl (S. Jarosz).
0957-4166/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tetasy.2012.10.003

M. A. Potopnyk et al. / Tetrahedron: Asymmetry 23 (2012) 1474–1479
1475
Table 1
2. Results and discussion
2.1. Synthesis
Synthesis of macrocyclic receptors 9a-f
R
N
8
8'
7'
7
O
O
The ‘fructose’ terminal OH (60-OH) group in the free,12 as well as
partially protected sucroses8,10a can be protected regioselectively
with silylating agents; this opens up a route for selective manipu-
lation at either ‘end’ via sequential reactions, first at the glucose
then at the fructose terminal positions. We also found that the ‘glu-
cose end’ (6-OH) shows a high affinity toward alkylating agents;
treatment of 1 with chloroacetonitrile preferentially gives monoal-
cohol 4.13 This feature (selective alkylation of 1 at the ‘glucose’
end) was assigned as a key-reaction in our strategy to prepare
the 16-membered sucrose-based aza-crowns.
6
5
K2CO3,
6'
BnO
1'
8
R
X
+
O
O
1
BnO
5'
DMF,
100°C,
4h
4
3
2'
4'
3'
2
O
OBn
BnO
OBn
OBn
9a-f
Entry
R
X
11
Yield (%)
1
2
3
4
5
6
Bn
Br
Cl
Br
Br
Br
Br
9a (=2b)
73
77
65
68
72
67
4-MeO-C6H4-CH2
Pyridine-2-ylmethyl
Allyl
MeOC(O)CH2
MeOCH2CH2
9b
9c
9d
9e
9f
The free hydroxyl group at the 60-carbon atom of 6-O-(cyanom-
ethyl)-10,2,3,30,4,40-hexa-O-benzylsucrose 4 was alkylated with
tert-butyl bromoacetate under catalytic phase-transfer conditions
(PTC) to provide the cyano-ester 5 in excellent yield. Both, the cy-
ano and ester groups in 5 were reduced with LiAlH4 to furnish the
corresponding amino alcohol 6, which was used as a starting mate-
rial for the preparation of macrocyclic derivatives. The reaction of 6
with iodine/triphenylphosphine/imidazole in refluxing toluene
afforded the iodo-sucrose derivative 7, which underwent sponta-
neous cyclization to 8 (79%; Scheme 1).
Receptors 9a-f were employed in the enantioselective recogni-
tion of chiral ammonium cations.
2.2. Enantioselective recognition
In the complexation of primary ammonium cations by aza-
crown ethers, polar N+-HꢂꢂꢂN and N+–Hꢂ ꢂ ꢂO hydrogen bond interac-
tions are the most important. Additionally, electrostatic interac-
tions between the cation and the electronegative centers of the
ligand take place and if the ammonium cation and receptor contain
an aromatic moiety, the p–p interactions are possible. In a first set
of complexation experiments, we evaluated the sucrose-based
macrocyclic ligand library 9a-f in recognition of the (S)- and (R)-
highly selective
silylation ref. 8
selective
alkylation ref. 13
CN
OH
HO
6'
O
6
HO
6
BnO
6'
i.
O
1'
O
BnO
Glu
Fruc
O
OBn
OBn
a-phenylethylammonium chloride, (S)-PEAꢂHCl, and (R)-PEAꢂHCl.
4
BnO
The association constant (Ka) was determined by the NMR titration
method14 in CDCl3. As shown in Table 2, all of the receptors
showed a much higher affinity toward the (S)-enantiomer (as in
the case of perbenzylated derivative 2c11), but contrary to 2c, the
(R)-isomer was not complexed. The only exception was receptor
9c, which contained a pyridine unit at the ring nitrogen atom,
and which showed a significant affinity for the (R)-isomer of
PEAꢂHCl (Ka = 67 Mꢁ1 entry 3 in Table 2). Moreover, an additional
ethylenoxy unit placed at the ring nitrogen atom 9f increased the
Ka value (as compared to ‘neutral’ benzylated derivative 9a) by
one order of magnitude. The model 1H NMR titration curve for 9f
is shown in Fig. 3.
1
OBn
ii.
NH2 HO
CO2t-Bu
CN
O
O
6
iii.
O
6'
O
6
6'
Glu Fruc
Glu Fruc
6
5
H
iv.
I
N
NH2
O
6
O
6'
O
6'
O
6
Table 2
Stability constants for complexes of ligands 9a-f with (S)- and (R)-phenylethylam-
monium chloride in CDCl3
Glu Fruc
Glu Fruc
8
Receptor
Ka, (S), M-1
70
140 10
317 33
427 42
623 48
733 69
Ka, (R), M-1
7
9a
9b
9c
9d
9e
9f
7
a*
a
Scheme 1. Synthesis of macrocyclic compound 8. (i) Ref.13; (ii) BrCH2CO2tBu, 50%
NaOH/toluene, Bu4NBr (cat.), rt, 1 h, 93%; (iii) LiAlH4, THF, ꢁ78 °C, 2 h, 88%; (iv)
Ph3P, imidazole, I2, toluene, reflux 4 h, 79%.
67
a
6
a
a
*
a — No signal shift observed in the NMR during titration.
The presence of the secondary amine functionality in the mac-
rocyclic ring (contrary to the previously prepared 2b9a) allowed us
to modify the steric and/or electronic properties of the ring. The
reaction of amine 8 with the corresponding alkyl halides provided
the respective derivatives 9a-f in good yields. It was possible to
introduce several different substituents, namely benzyl-, 4-
methoxybenzyl-, pyridine-2-ylmethyl-, allyl-, 2-methoxy-2-oxo-
ethyl-, and 2-methoxyethyl (Table 1).
Lariat ether 9f, which showed the highest Ka value toward the
(S)- -phenylethylammonium chloride, was selected as a model
to study the complexation abilities of such types of receptors to-
ward the amino acid derivatives. Four pairs (alanine, valine, phen-
ylglycine, and phenylalanine) of enantiomeric methyl ester
ammonium salts (Fig. 2) were chosen.
a

1476
M. A. Potopnyk et al. / Tetrahedron: Asymmetry 23 (2012) 1474–1479
nine formed much weaker complexes. However, while the enanti-
oselectivity of the complexation was low, it showed some
regularity; the -aminoacid derivatives formed stronger complexes
than the -enantiomers (Table 3).
O
O
Me
Me
Me
Me
OMe
NH3+Cl-
OMe
NH3+Cl-
D
NH3+Cl-
NH3+Cl-
L
We have also studied the complexation of these amino acid
methyl ester hydrochlorides with the receptor 9f in DMSO. The
results are shown in Table 3. Although the Ka values were much
lower (than in CDCl3/CD3OD), we observed good enantioselectivity
for alanine and regularity in a preferential complexation of all four
(S)-PEA·HCl
Me
(R)-PEA·HCl
Me
L-Ala-OMe·HCl
D-Ala-OMe·HCl
O
O
O
Me
OMe
NH3+Cl-
Me
OMe
NH3+Cl-
OMe
NH3+Cl-
unnatural D-amino acid derivatives.
L-Val-OMe·HCl
O
D-Val-OMe·HCl
O
L-Phg-OMe·HCl
O
3. Conclusion
In conclusion, we have designed and synthesized a series of no-
vel sucrose-based macrocyclic receptors starting from compounds
with a secondary amine functionality in the ring. This feature al-
lowed us to introduce various substituents at this N-atom which
made it possible to tune the electronic properties of the macrocy-
cle. These compounds showed high enantioselectivity toward
OMe
NH3+Cl-
OMe
NH3+Cl-
OMe
NH3+Cl-
D-Phg-OMe·HCl
L-Phe-OMe·HCl
D-Phe-OMe·HCl
Figure 2. Structures of the ammonium guests.
(S)-a-phenylethylamine. Compound 9f, which has 2-methoxy-
ethyl-moieties at the ring-nitrogen atom, also exhibited satisfac-
tory enantioselectivity toward amino acid methyl ester
hydrochlorides in CDCl3–CD3OD as well as DMSO-d6.
0.00
-0.02
-0.04
-0.06
-0.08
-0.10
-0.12
4. Experimental
4.1. General
NMR spectra were recorded with a Bruker DRX 500 MHz and a
Varian VNMRS 600 MHz spectrometers for solutions in CDCl3
(internal Me4Si) unless otherwise stated. Most of the resonances
were assigned by COSY (1H–1H), HSQC (1H–13C), and HMBC
(1H-13C) correlations. The 1H- and 13C-aromatic resonances occur-
ring at the typical d values were omitted for simplicity. Mass spec-
tra were recorded with an ESI/MS Mariner (PerSeptive Biosystem)
mass spectrometer. Optical rotations were measured with a Digital
Jasco polarimeter DIP-360 for solutions in CHCl3 or CH2Cl2 (c, 1).
Column and flash chromatography was performed on silica gel
(Merck, 230–400 mesh). Organic solutions were dried over anhy-
drous magnesium sulfate.
0.00
0.01
0.02
0.03
0.04
CG, mol/L
4.2. Synthesis of 10,2,3,30,4,40-hexa-O-benzyl-60-O-(2-tert-but-
oxy-2-oxoethyl)-6-O-cyanomethylsucrose 5
Figure 3. Titration curve for macrocycle 9f and (S)-(ꢁ)-phenylethylammonium
chloride. The shift of the signal of the anomeric proton of the sucrose was followed
during the experiment.
To a solutionof alcohol4 (2.030 g,2.20 mmol)intoluene(100 mL),
tetrabutylammonium bromide (0.142 mg, 0.44 mmol) was added,
followed by 50% aqueous NaOH (100 mL). A solutionof tert-butylbro-
moacetate (0.780 mL, 5.28 mmol) in toluene (10 mL) was added and
the mixture was stirred vigorously at room temperature for 15 h. The
layers were separated, and the organic phase was washed with water
(50 mL) and brine (50 mL), dried, concentrated, and the product was
isolated by column chromatography (hexane–ethyl acetate, 5:1) to
afford pure 5 (2.123 g, 2.05 mmol, 93%). TLC (hexane/AcOEt (3:1))
The association constants in CDCl3/CD3OD (Table 3) were much
higher for these amino acid derived salts than for simple phenyl-
ethylamine. The highest Ka value was observed for valine methyl
ester hydrochloride (Val-OMeꢂHCl). Less sterically demanding ala-
Table 3
Rf = 0.39. Yellowish oil.
½
a 2D1
ꢃ
¼ þ40:4 (c 1, CHCl3). 1H NMR
Stability constants for complexes of ligand 9f with amino acid methyl ester
hydrochlorides in CDCl3–CD3OD (80:20) or DMSO-d6
(500 MHz) d: 7.13–7.37 (m, 30H, H-Ar), 5.81 (d, 1H, J1,2 = 3.4 Hz, H-
1), 2.96–4.95 (range of multiplets, aliphatic hydrogens of the sucrose
skeleton and the macrocyclic ring), 1.54 (s, 9H, CO2C(CH3)3). 13C NMR
(125 MHz) d: 169.59 (CO2tBu), 139.12, 138.75, 138.57 (double inten-
sity), 138.41, 138.17 (Cquat, 6 ꢀ OCH2Ph), 116.27 (CN), 104.96 (C-20),
89.97 (C-1), 84.08, 82.16 (double intensity), 82.03, 81.98, 80.04,
79.77, 70.12 (C-2,3,30,4,40,5,50, C(CH3)3), 75.87, 75.24, 73.80, 73.40,
73.38, 72.76, 72.52, 71.74, 70.53, 69.27 (6 ꢀ OCH2Ph, OCH2CO2tBu,
C-10, C-6, C-60), 56.90 (CH2CN), 26.47 (C(CH3)3). HR MS (ESI) calcd
for C62H69NO13Na [M+Na]+ 1058.4661, found 1058.4673. Analysis
for C62H69NO13 (1036.21): Calcd: C, 71.86; H, 6.71; N, 1.35. Found:
C, 71.90; H, 6.53; N, 1.29.
Guest
CDCl3–CD3OD (80:20)
Ka, Mꢁ1
KD/KL
1655 164 2.02
DMSO-d6
Ka, Mꢁ1
KD/KL
32.4 2.2
16.2 1.2
301 28
206 7.0
145 10
100 10
162 11
127 7.0
2.00
D
-Ala-OMeꢂHCl
-Ala-OMeꢂHCl
-Val-OMeꢂHCl
-Val-OMeꢂHCl
-Phg-OMeꢂHCl
-Phg-OMeꢂHCl
-Phe-OMeꢂHCl
-Phe-OMeꢂHCl
820 50
14740 990
14380 1500
5510 490
4020 350
3835 150
3390 220
L
1.03
1.37
1.13
1.46
1.45
1.28
D
L
D
L
D
L

M. A. Potopnyk et al. / Tetrahedron: Asymmetry 23 (2012) 1474–1479
1477
4.3. Synthesis of 6-O-(2-aminoethyl)-10,2,3,30,4,40-hexa-O-benz-
yl-60-O-(2-hydroxyethyl)-sucrose 6
m, H-70), 3.70 (1H, dd, J6,6 11.7 Hz, J6,5 2.8 Hz, H-6), 3.61–3.69
(2H, m, H-70, H-7), 3.60 (1H, d, J10,10 10.7 Hz, H-10), 3.51–3.59
(3H, m, H-60, H10, H-4), 3.42 (1H, dd, H-2), 3.16 (1H, dd, H-6),
2.92–2.97 (2H, m, H-8, H-80), 2.86 (1H, m, H-80), 2.79 (1H, m, H-
8). 13C NMR (150 MHz) d 138.81, 138.55, 138.52, 138.04, 137.85,
137.66 (Cquat, 6 ꢀ OCH2Ph), 103.63 (C-20), 88.28 (C-1), 84.02 (C-
30), 81.30 (C-3), 79.12 (C-2), 78.79 (C-50), 78.69 (C-40), 77.27 (C-
4), 75.31, 74.61, 73.41, 72.74, 72.55, 72.46 (6 ꢀ OCH2Ph), 73.44
(C-10), 71.50 (C-5), 71.06 (C-6), 68.62 (C-60), 67.20 (C-7), 65.30
(C-70), 49.18 (C-8), 47.59 (C-80). HR MS (ESI) calcd for C58H65NO11-
Na [M+Na]+ 974.4450, found 974.4463. Analysis for C58H65NO11
(952.16): Calcd: C, 73.16; H, 6.88; N, 1.47. Found: C, 73.38; H,
6.73; N, 1.32.
To
a cooled (–78 °C) solution of compound 5 (2.053 g,
1.98 mmol) in dry THF (200 mL), LiAlH4 (0.602 g, 15.85 mmol)
was added slowly within 15 min. The mixture was then allowed
to reach room temperature and stirred for 10 h. The excess hydride
was carefully decomposed with water (50 mL) and aqueous potas-
sium bisulfate (KHSO4, 100 mL). Ethyl acetate (300 mL) was then
added, the layers were separated, and the aqueous layer was ex-
tracted with ethyl acetate (3 ꢀ 150 mL). The combined organic lay-
ers were dried, concentrated, and the product was isolated by flash
chromatography (dichloromethane–methanol, 91:9) to afford pure
6 (1.692 g, 1.74 mmol, 88%). TLC (AcOEt/MeOH/H2O (45:5:3))
Rf = 0.12. Yellowish oil.
½
a 2D3
ꢃ
¼ þ54:0 (c 1, CHCl3). 1H NMR
4.5. General procedure for the synthesis of receptors 9a–f
(600 MHz) d: 7.40–7.37 (30H, m ArH), 5.92 (1H, d, J1,2 3.7 Hz, H-
1), 4.92 (1H, d, J 11.0 Hz, benzylic H), 4.82 (1H, d, J 11.2 Hz, benzylic
H), 4.75 (1H, d, J 11.0 Hz, benzylic H), 4.71 (1H, d, J 11.9 Hz, benzylic
H), 4.65 (1H, d, J 11.7 Hz, benzylic H), 4.64 (1H, d, J 11.3 Hz, benzylic
H), 4.63 (1H, d, J 12.1 Hz, benzylic H), 4.61 (1H, d, J 12.1 Hz, benzylic
H), 4.59 (1H, d, J 11.7 Hz, benzylic H), 4.52 (1H, d, J 11.2 Hz, benzylic
H), 4.47 (1H, d, J 11.3 Hz, benzylic H), 4.46 (1H, d, J 11.9 Hz, benzylic
To a solution of compound 8 (190 mg, 0.20 mmol) in dry DMF
(15 mL), K2CO3 (56 mg, 0.40 mmol) was added followed by the cor-
responding alkyl halide (0.40 mmol). The mixture was stirred for
4 h at 100 °C and then cooled to rt. Water (50 mL) was added,
the organic phase was separated, and the aqueous phase extracted
with AcOEt (4 ꢀ 50 mL). The combined organic solutions were
washed with water (2 ꢀ 30 mL), brine (30 mL), dried, concentrated,
and the product was isolated by flash chromatography (hexane–
ethyl acetate, 1:1 to 0:1) to afford pure 9a–f.
0
0
H), 4.45 (1H, d, J03 8.1 Hz, H-3 ), 4.39 (1H, dd, J4 ,5 8.1 Hz, H-4 ), 4.07
0
0
,40
(1H, m H-5), 3.99 (1H, m, H-50), 3.92 (1H, dd, J3,2 9.3 Hz, J3,4 9.2 Hz,
H-3), 3.78 (1H, dd, J6 ,6 11.0 Hz, J6 ,5 2.7 Hz, H-60), 3.69 (1H, d, J1 ,1
0
0
0
0
0
0
10.8 Hz, H-10), 3.60 (1H, dd, J6 ,5 4.2 Hz, H-60), 3.56 (1H, d, H-10),
3.50–3.55 (2H, m, H-4, H-80), 3.42–3.49 (4H, m, 2H-70, H-80, H-2),
3.38 (1H, m, H-7), 3.28–3.33 (2H, m, 2H-6), 3.27 (1H, m, H-7),
2.78–2.88 (2H, m, 2H-8). 13C NMR (150 MHz) d: 138.97, 138.57,
138.20, 138.14, 138.06, 137.86 (Cquat, 6 ꢀ Ph), 104.09 (C-20), 88.76
(C-1), 83.66 (C-30), 81.81 (C-3), 80.26 (C-40), 79.40 (C-2), 78.96 (C-
50), 77.37 (C-4), 75.28, 74.69, 73.39, 72.77, 72.60, 72.20
(6 ꢀ OCH2Ph), 72.50 (C-70), 72.16 (C-10), 71.06 (C-7), 70.56 (C-5),
70.04 (C-60), 69.11 (C-6), 61.35 (C-80), 40.94 (C-8). HR MS (ESI) calcd
for C58H68O12 [M+H+] 970.4736, found 970.4715. Analysis for
0
0
4.5.1. 6,60-(3-Azabenzylpenta-1,5-di-yl)-10,2,3,30,4,40-hexa-O-ben-
zylsucrose 9a
TLC (AcOEt/MeOH/H2O–45:5:3) Rf = 0.71. Yellowish oil.
½
a 2D2
ꢃ
¼ þ28:1 (c 1, CHCl3). 1H NMR (600 MHz) d: 7.15–7.35 (35H,
m ArH), 5.43 (1H, d, J1,2 3.2 Hz, H-1), 4.87 (1H, d, J 11.1 Hz, benzylic
H), 4.86 (1H, d, J 10.9 Hz, benzylic H), 4.71 (1H, d, J 10.9 Hz, ben-
zylic H), 4.70 (1H, d, J 11.6 Hz, benzylic H), 4.69 (1H, d, J 12.0 Hz,
benzylic H), 4.67 (1H, d, J 11.1 Hz, benzylic H), 4.65 (1H, d, J
11.6 Hz, benzylic H), 4.62 (1H, d, J 11.5 Hz, benzylic H), 4.52 (2H,
d, J 11.5 Hz, benzylic H), 4.44 (1H, d, J 12.0 Hz, benzylic H), 4.43
C
58H67NO12ꢂH2O (988.17): Calcd: C, 70.50; H, 7.04; N, 1.42. Found:
(1H, d, J3 ,4 7.2 Hz, H-30), 4.25 (1H, d, J 11.8 Hz, benzylic H), 4.23
0
0
C, 70.37; H, 7.10; N, 1.37.
(1H, m, H-5), 4.19 (1H, dd, J4 ,5 7.2 Hz, H-40), 4.04–4.09 (2H, m,
0
0
4.4. Synthesis of 6,60-(3-azapenta-1,5-di-yl)-10,2,3,30,4,40-hexa-O-
H-3, H-50), 3.91 (1H, dd, J5 ,6 6.5 Hz, J6 ,6 10.0 Hz, H-60), 3.81 (1H,
0
0
0
0
dd, J5 ,6 5.9 Hz, H-60), 3.65–3.72 (2H, m, H-6, H-70), 3.60–3.64
(2H, m, H-10, H-70), 3.59 (2H, s, 2H-9), 3.44–3.52 (4H, m, H-2, H-
10, 2H-7), 3.42 (1H, ddd, J5,6 7.9 Hz, J5,6 8.0 Hz, J6,6 10.3 Hz, H-6),
3.20 (1H, dd, J 9.1 Hz, J 9.4 Hz, H-4), 2.88 (1H, m, H-8’), 2.65–2.78
(3H, m, 2H-8, H-80). 13C NMR (150 MHz) d: 139.47, 138.76,
138.65, 138.55, 138.24, 138.03, 137.96 (Cquat, 7 ꢀ Ph), 104.13 (C-
20), 90.09 (C-1), 84.91 (C-40), 83.65 (C-3’), 81.63 (C-3), 79.99 (C-
50), 79.95 (C-2), 79.45 (C-4), 75.46, 74.79, 73.45, 73.15, 72.74,
72.14 (6 ꢀ OCH2Ph), 72.19 (C-60), 71.70 (C-6), 71.03 (C-10), 70.93
(C-5), 70.72 (C-7), 69.06 (C-7’), 60.37 (C-9), 53.51 (C-80), 53.15
(C-8). HR MS (ESI) calcd for C65H72NO11 [M+H]+ 1042.5099, found
1042.5077. Analysis for C65H71NO11 (1042.29): Calcd: C, 74.90; H,
6.87; N, 1.34. Found: C, 74.87; H, 6.79; N, 1.38.
0
0
benzylsucrose 8
Compound 6 (1.550 g, 1.60 mmol) in toluene (300 mL) was
heated at reflux with PPh3 (0.503 g, 1.92 mmol) for 10 min and
cooled to 80 °C. Imidazole (0.544 g, 7.99 mmol) was added, fol-
lowed by the slow addition (during 10 min) of a solution of iodine
(0.527 g, 2.08 mmol) in toluene (50 mL), and the mixture was
heated at reflux for 4 h, after which it was concentrated and the
residue was taken up in ethyl acetate (100 mL) and water
(50 mL). The layers were separated and the aqueous one was ex-
tracted with ethyl acetate (3 ꢀ 50 mL). The combined organic solu-
tions were washed with saturated aq. Na2S2O3 (50 mL) and water
(30 mL), dried, concentrated, and the product was isolated by col-
umn chromatography (ethyl acetate, then ethyl acetate–methanol,
10:1) to afford macrocycle 8 (1.205 g, 1.27 mmol, 79%). TLC (AcOEt/
4.5.2. 6,60-[3-Aza(4-methoxybenzyl)penta-1,5-di-yl]-10,2,3,30,4,
40-hexa-O-benzylsucrose 9b
MeOH/H2O–45:5:3) Rf = 0.29. Yellowish oil. ½a D23
¼ þ38:9 (c 1,
ꢃ
CHCl3). 1H NMR (600 MHz) d: 7.16–7.40 (30H, m, ArH), 5.83 (1H,
d, J1,2 3.7 Hz, H-1), 4.92 (1H, d, J 10.9 Hz, benzylic H), 4.87 (1H, d,
J 11.9 Hz, benzylic H), 4.81 (1H, d, J 11.9 Hz, benzylic H), 4.81
(1H, d, J 11.3 Hz, benzylic H), 4.77 (1H, d, J 10.9 Hz, benzylic H),
4.69 (1H, d, J 11.7 Hz, benzylic H), 4.64 (1H, d, J 12.1 Hz, benzylic
H), 4.63 (1H, d, J 11.7 Hz, benzylic H), 4.62 (1H, d, J 11.0 Hz, ben-
TLC (AcOEt/MeOH/H2O–45:5:3) Rf = 0.48. Yellowish oil.
½
a 1D9
ꢃ
¼ þ17:3 (c 1, CHCl3). 1H NMR (600 MHz) d: 7.18–7.35 (32H,
m ArH), 6.78 (2H, d, J 8.7 Hz, ArH), 5.44 (1H, d, J1,2 3.1 Hz, H-1),
4.87 (1H, d, J 11.2 Hz, benzylic H), 4.86 (1H, d, J 10.8 Hz, benzylic
H), 4.72 (1H, d, J 11.2 Hz, benzylic H), 4.71 (1H, d, J 11.9 Hz, ben-
zylic H), 4.69 (1H, d, J 11.9 Hz, benzylic H), 4.68 (1H, d, J 12.5 Hz,
benzylic H), 4.65 (1H, d, J 11.9 Hz, benzylic H), 4.62 (1H, d, J
11.5 Hz, benzylic H), 4.54 (1H, d, J 11.2 Hz, benzylic H), 4.53 (1H,
d, J 11.5 Hz, benzylic H), 4.44 (1H, d, J 12.5 Hz, benzylic H), 4.43
0
0
zylic H), 4.53 (1H, d, J 11.3 Hz, benzylic H), 4.50 (1H, d, J3 ,4
8.1 Hz, H-30), 4.48 (1H, d, J 12.1 Hz, benzylic H), 4.43 (1H, d, J
11.0 Hz, benzylic H), 4.34 (1H, dd, J4 ,5 8.6 Hz, H-40), 4.23 (1H,
ddd, J5,4 10.1 Hz, J5,6 2.8 Hz, J5,6 1.6 Hz, H-5), 3.92–3.99 (3H, m, H-
50, H-7, H-60), 3.90 (1H, dd, J3,2 9.7 Hz, J3,4 8.9 Hz, H-3), 3.86 (1H,
0
0
(1H, d, J3 ,4 7.0 Hz, H-30), 4.25 (1H, d, J 11.8 Hz, benzylic H), 4.24
0
0
(1H, m, H-5), 4.20 (1H, dd, J4 ,5 7.0 Hz, H-40), 4.05–4.09 (2H, m,
0
0

1478
M. A. Potopnyk et al. / Tetrahedron: Asymmetry 23 (2012) 1474–1479
H-3, H-50), 3.92 (1H, m, H-60), 3.81 (1H, m, H-60), 3.71 (3H, s, OCH3),
H-80). 13C NMR (150 MHz) d: 138.78, 138.67, 138.56, 138.27,
138.04, 137.95 (Cquat
3.66–3.71 (2H, m, H-6, H-70), 3.62 (1H, d, J1 ,1 11.2 Hz, H-10), 3.61
(1H, m, H-70), 3.53 (2H, s, 2H-9), 3.45–3.51 (4H, m, H-2, H-10, 2H-
7), 3.42 (1H, m, H-6), 3.21 (1H, dd, J 9.4 Hz, J 9.8 Hz, H-4), 2.85
(1H, m, H-80), 2.64–2.77 (3H, m, 2H-8, H-80). 13C NMR (150 MHz)
d: 158.57 (CAr-OMe), 138.79, 138.68, 138.59, 138.27, 138.05,
137.98 (Cquat, 6 ꢀ Ph), 104.15 (C-20), 90.13 (C-1), 84.97 (C-40),
83.68 (C-30), 81.66 (C-3), 80.02 (C-50), 79.98 (C-2), 79.47 (C-4),
75.48, 74.82, 73.47, 73.17, 72.78, 72.17 (6 ꢀ OCH2Ph), 72.21 (C-
60), 71.76 (C-6), 71.07 (C-10), 70.99 (C-5), 70.81 (C-7), 69.09 (C-
70), 59.71 (C-9), 55.17 (OCH3), 53.38 (C-80), 53.06 (C-8). HR MS
(ESI) calcd for C66H74NO12 [M+H]+ 1072.5206, found 1072.5221.
Analysis for C66H73NO12 (1072.32): Calcd: C, 73.93; H, 6.86; N,
1.31. Found: C, 73.90; H, 6.65; N, 1.32.
,
6 ꢀ Ph), 135.87 (C-10), 117.37 (C-11),
0
0
104.13 (C-20), 90.14 (C-1), 84.87 (C-40), 83.67 (C-30), 81.62 (C-3),
79.95 (C-2), 79.90 (C-50), 79.45 (C-4), 75.47, 74.82, 73.45, 73.17,
72.74 (5 ꢀ OCH2Ph), 72.21 (C-60), 72.15 (OCH2Ph), 71.79 (C-6),
70.94 (C-5), 70.92 (C-10), 70.59 (C-7), 68.92 (C-70), 59.06 (C-9),
54.14 (C-80), 53.12 (C-8). HR MS (ESI) calcd for C61H70NO11
[M+H]+ 992.4943, found 992.4977. Analysis for C61H69NO11
(992.23): Calcd: C, 73.84; H, 7.01; N, 1.41. Found: C, 73.69; H,
7.12; N, 1.45.
4.5.5. 6,60-[3-Aza(2-methoxy-2-oxoethyl)penta-1,5-di-yl]-10,2,3,
30,4,40-hexa-O-benzylsucrose 9e
TLC (AcOEt/MeOH/H2O–45:5:3) Rf = 0.37. Yellowish oil.
½
a 2D3
ꢃ
¼ þ24:6 (c 1, CH2Cl2). 1H NMR (600 MHz) d: 7.19–7.35 (30H,
4.5.3. 6,60-[3-Aza(pyridine-2-ylmethyl)penta-1,5-di-yl]-10,2,3,30,
m, Ar-H), 5.41 (1H, d, J1,2 3.2 Hz, H-1), 4.86 (1H, d, J 11.4 Hz, ben-
zylic H), 4.85 (1H, d, J 11.0 Hz, benzylic H), 4.64–4.72 (5H, m, ben-
zylic H), 4.61 (1H, d, J 11.6 Hz, benzylic H), 4.53 (1H, d, J 11.1 Hz,
benzylic H), 4.51 (1H, d, J 11.7 Hz, benzylic H), 4.44 (1H, d, J
4,40-hexa-O-benzylsucrose 9c
TLC
(AcOEt/MeOH/H2O–45:5:3)
Rf = 0.36.
Yellow
oil.
½
a 2D4
ꢃ
¼ þ21:9 (c 1, CH2Cl2). 1H NMR (600 MHz) d: 8.47 (1H, m,
12.1 Hz, benzylic H), 4.41 (1H, d, J3 ,4 7.2 Hz, H-30), 4.27 (1H, d, J
0
0
Py-H), 7.53 (1H, td, J 7.8 Hz, J 1.7 Hz, Py-H), 7.50 (1H, t, J 7.8 Hz,
Py-H), 7.19–7.34 (30H, m, Ar-H), 7.80 (1H, m, Py-H), 5.44 (1H, d,
J1,2 3.2 Hz, H-1), 4.86 (1H, d, J 11.1 Hz, benzylic H), 4.85 (1H, d, J
10.9 Hz, benzylic H), 4.71 (1H, d, J 11.0 Hz, benzylic H), 4.70 (1H,
d, J 11.2 Hz, benzylic H), 4.69 (1H, d, J 11.6 Hz, benzylic H), 4.65
(2H, s, benzylic H), 4.62 (1H, d, J 11.5 Hz, benzylic H), 4.52 (2H, d,
J 11.3 Hz, benzylic H), 4.44 (1H, d, J 12.0 Hz, benzylic H), 4.43
0
0
12.0 Hz, benzylic H), 4.21 (1H, m, H-5), 4.15 (1H, dd, J4 ,5 7.2 Hz,
H-40), 4.03–4.07 (2H, m, H-3, H-50), 3.91 (1H, dd, J6 ,6 10.1 Hz,
0
0
J5 ,6 6.4 Hz, H-60), 3.78 (1H, dd, J5 ,6 5.9 Hz, H-60), 3.67–3.71 (2H,
m, H-6, H-70), 3.65 (3H, s, CH3), 3.57–3.63 (2H, m, H-7, H-70),
3.44–3.51 (4H, m, H-2, H-7, 2H-10), 3.39–3.43 (1H, m, H-6), 3.39
(2H, s, 2H-9), 3.20 (1H, dd, J 10.1 Hz, J 9.0 Hz, H-4), 3.00–3.06
(1H, m, H-80), 2.79–2.93 (3H, m, 2H-8, H-80). 13C NMR (150 MHz)
d: 171.97 (CO2Me), 138.79, 138.69, 138.58, 138.28, 138.07,
137.96 (Cquat, 6 ꢀ Ph), 104.09 (C-20), 90.10 (C-1), 84.76 (C-40),
83.65 (C-30), 81.66 (C-3), 79.95 (C-2), 79.92 (C-50), 79.42 (C-4),
75.49, 74.82, 73.44, 73.20, 72.71 (5 ꢀ OCH2Ph), 72.25 (C-60),
72.16 (OCH2Ph), 71.75 (C-6), 70.97 (C-7), 70.86 (C-5), 70.08
(C-10), 69.07 (C-70), 55.76 (C-9), 59.06 (C-9), 53.93 (C-80), 53.42
(C-8), 51.28 (OCH3). HR MS (ESI) calcd for C61H69NO13 [M+Na]+
1046.4661, found 1046.4656. Analysis for C61H69NO11 (1024.23):
Calcd: C, 71.53; H, 6.79; N, 1.37. Found: C, 71.75; H, 6.92; N,
1.46.
0
0
0
0
(1H, d, J3 ,4 7.1 Hz, H-30), 4.26 (1H, d, J 12.1 Hz, benzylic H), 4.23
0
0
(1H, m, H-5), 4.18 (1H, dd, J4 ,5 7.1 Hz, H-40), 4.04–4.09 (2H, m,
0
0
H-3, H-50), 3.91 (1H, dd, J5 ,6 6.4 Hz, J6 ,6 9.1 Hz, H-60), 3.83 (1H,
0
0
0
0
dd, J5 ,6 6.0 Hz, H-60), 3.79 (1H, d, J 14.7 Hz, H-9), 3.75 (1H, d, J
14.7 Hz, H-9), 3.69–3.73 (1H, m, H-70), 3.62–3.67 (2H, m, H-6, H-
70), 3.61 (1H, d, J 11.0 Hz, H-10), 3.46–3.51 (4H, m, H-2, H-10, 2H-
7), 3.39 (1H, dd, J5,6 8.3 Hz, J6,6 10.2 Hz, H-6), 3.19 (1H, dd, J
9.1 Hz, J 9.9 Hz, H-4), 2.92–2.96 (1H, m, H-80), 2.75–2.80 (3H, m,
2H-8, H-80). 13C NMR (150 MHz) d: 159.97 (C-Py), 148.77 (C-Py),
138.71, 138.63, 138.47, 138.19, 138.01, 137.91 (Cquat, 6 ꢀ Ph),
136.45 (C-Py), 136.03 (C-Py), 123.08 (C-Py), 121.87 (C-Py), 104.18
(C-20), 90.22 (C-1), 84.88 (C-40), 83.70 (C-30), 81.63 (C-3), 79.99
(C-50), 79.96 (C-2), 79.48 (C-4), 75.48, 74.86, 73.50, 73.19, 72.69
(5 ꢀ OCH2Ph), 72.39 (C-60), 72.17 (OCH2Ph), 71.78 (C-6), 71.00 (C-
10), 70.99 (C-5), 70.36 (C-7), 68.96 (C-70), 61.97 (C-9), 54.02 (C-
8’), 53.51 (C-8). HR MS (ESI) calcd for C64H71N2O11 [M+H]+
1043.5052, found 1043.5067. Analysis for C64H70N2O11 (1043.28):
Calcd: C, 73.68; H, 6.76; N, 2.69. Found: C, 73.91; H, 6.62; N, 2.75.
0
0
4.5.6. 6,60-[3-Aza(2-methoxyethyl)penta-1,5-di-yl]-10,2,3,30,4,40-
hexa-O-benzylsucrose 9f
TLC (AcOEt/MeOH/H2O (45:5:3)) Rf = 0.33. Yellowish oil.
½
a 2D2
ꢃ
¼ þ31:7 (c 1, CHCl3). 1H NMR (600 MHz) d: 7.17–7.35 (30H,
m ArH), 5.41 (1H, d, J1,2 3.3 Hz, H-1), 4.87 (1H, d, J 11.0 Hz, benzylic
H), 4.86 (1H, d, J 10.8 Hz, benzylic H), 4.70 (1H, d, J 11.1 Hz, ben-
zylic H), 4.69 (1H, d, J 11.5 Hz, benzylic H), 4.68 (1H, d, J 10.8 Hz,
benzylic H), 4.66 (2H, d, J 11.8 Hz, benzylic H), 4.61 (1H, d, J
11.5 Hz, benzylic H), 4.54 (1H, d, J 11.1 Hz, benzylic H), 4.51 (1H,
d, J 11.8 Hz, benzylic H), 4.44 (1H, d, J 12.0 Hz, benzylic H), 4.41
4.5.4. 6,60-[3-Aza(prop-2-en-1-yl)penta-1,5-di-yl]-10,2,3,30,4,40-
hexa-O-benzylsucrose 9d
TLC (AcOEt/MeOH/H2O
- 45:5:3) Rf = 0.39. Yellowish oil.
a 2D3
ꢃ
¼ þ29:1 (c 1, CHCl3). 1H NMR (600 MHz) d: 7.19–7.35 (30H,
(1H, d, J3 ,4 7.2 Hz, H-30), 4.25 (1H, d, J 12.0 Hz, benzylic H), 4.20
0
0
½
m, Ar-H), 5.80 (1H, ddt, J10,11 17.1 Hz, J10,11 10.2 Hz, J10,9 6.5 Hz,
(1H, m, H-5), 4.14 (1H, dd, J4 ,5 7.0 Hz, H-40), 4.03–4.10 (2H, m,
0
0
0
H-10), 5.42 (1H, d, J1,2 3.2 Hz, H-1), 5.12 (1H, dd, J11,11 1.3 Hz, H-
H-3, H-50), 3.86 (1H, dd, J5 ,6 6.5 Hz, J6 ,6 10.0 Hz, H-60), 3.79 (1H,
0
0
0
0
0
110), 5.12 (1H, dd, H-11), 4.87 (1H, d, J 10.9 Hz, benzylic H), 4.85
(1H, d, J 10.8 Hz, benzylic H), 4.71 (1H, d, J 10.8 Hz, benzylic H),
4.70 (1H, d, J 11.5 Hz, benzylic H), 4.69 (1H, d, J 11.8 Hz, benzylic
H), 4.67 (1H, d, J 11.3 Hz, benzylic H), 4.66 (1H, d, J 11.8 Hz, ben-
zylic H), 4.61 (1H, d, J 11.5 Hz, benzylic H), 4.54 (1H, d, J 10.9 Hz,
benzylic H), 4.52 (1H, d, J 11.3 Hz, benzylic H), 4.42 (1H, d, J
dd, J5 ,6 6.0 Hz, H-60), 3.67–3.72 (2H, m, H-6, H-70), 3.60–3.66
(2H, m, H-10, H-70), 3.49–3.53 (2H, m, 2H-7), 3.45–3.49 (2H, m,
H-10, H-2), 3.39–3.43 (3H, m, H-6, 2H-10), 3.28 (3H, s, 3H-11),
3.20 (1H, dd, J 9.4 Hz, J 9.6 Hz, H-4), 2.86–2.92 (1H, m, H-80),
2.74–2.79 (3H, m, H-80, 2H-8), 2.67 (2H, t, J 5.9 Hz, 2H-9). 13C
NMR (150 MHz) d: 138.78, 138.71, 138.58, 138.30, 138.07, 137.99
(Cquat, 6 ꢀ Ph), 104.19 (C-20), 90.14 (C-1), 84.80 (C-40), 83.74 (C-
30), 81.63 (C-3), 79.99 (C-2), 79.94 (C-50), 79.46 (C-4), 75.44,
74.79, 73.45, 73.20, 72.61, 72.19 (6 ꢀ OCH2Ph), 72.17 (C-60),
71.77 (C-6), 71.13 (C-10), 71.06 (C-10), 70.97 (C-5), 70.69 (C-7),
69.08 (C-70), 58.76 (C-11), 55.19 (C-9), 54.07 (C-8), 53.91 (C-80).
HR MS (ESI) calcd for C61H72NO12 [M+H]+ 1010.5049, found
1010.5003. Analysis for C61H71NO12 (1010.25): Calcd: C, 72.52; H,
7.08; N, 1.39. Found: C, 72.67; H, 7.19; N, 1.32.
0
0
12.1 Hz, benzylic H), 4.41 (1H, d, J3 ,4 7.1 Hz, H-30), 4.26 (1H, d, J
12.1 Hz, benzylic H), 4.21 (1H, m, H-5), 4.15 (1H, dd, J040;5 7.1 Hz,
0
0
H-40), 4.04–4.08 (2H, m, H-3, H-50), 3.88 (1H, dd, J6 ,6 10.1 Hz,
0
0
J5 ,6 6.4 Hz, H-60), 3.79 (1H, dd, J5 ,6 6.0 Hz, H-60), 3.67–3.73 (2H,
0
0
0
0
m, H-6, H-70), 3.62 (1H, d, J1 ,1 10.9 Hz, H-10), 3.61 (1H, m, H-70),
3.46–3.53 (4H, m, H-2, H-10, 2H-7), 3.42 (1H, dd, J6,6 10.4 Hz, J5,6
8.0 Hz, H-6), 3.21 (1H, dd, J 9.7 Hz, J 9.3 Hz, H-4), 3.09 (2H, d, J9,10
6.5 Hz, 2H-9), 2.81–2.86 (1H, m, H-80), 2.68–2.74 (3H, m, 2H-8,
0
0

M. A. Potopnyk et al. / Tetrahedron: Asymmetry 23 (2012) 1474–1479
1479
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Deniz, P.; Turgut, Y.; Togrul, M.; Hosgoren, H. Tetrahedron 2011, 67, 6227–6232.
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Chem. 2007, 72, 5709–5714; (b) Amato, M. E.; Ballistreri, F. P.; Gentile, S.;
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4.6. General procedure for the titration experiments
A solution of receptor 9a–f in 0.5 mL of the respective solvent
(CDCl3 for the experiments with phenylethylammonium chlorides;
CDCl3–CD3OD or DMSO-d6 for methyl ester amino acid hydrochlo-
ride) was prepared (concentration given separately for each
experiment). The NMR spectrum was recorded at room tempera-
ture. Small portions of the guest were then added to the solution.
After each addition of the ammonium salt, NMR spectra were re-
corded. The shift of the signal of anomeric proton of sucrose was
followed. The additions of the guest were continued until the con-
stant value of the chemical shift of H-1 (anomeric). The value of the
signal shift was then plotted against the concentration of the guest
in solution. A curve was fitted to the plot, using the empirical equa-
tion described by Fielding.14
8. Jarosz, S.; Mach, M. Eur. J. Org. Chem. 2002, 769–780.
Acknowledgments
9. (a) Jarosz, S.; Listkowski, A.; Lewandowski, B.; Ciunik, Z.; Brzuszkiewicz, A.
Tetrahedron 2005, 61, 8485–8492; (b) Jarosz, S.; Lewandowski, B. Carbohydr.
Res. 2008, 343, 965–969.
10. (a) Jarosz, S.; Lewandowski, B.; Listkowski, A. Synthesis 2008, 913–916; (b)
Lewandowski, B.; Jarosz, S. Org. Lett. 2010, 12, 2532–2535.
11. Lewandowski, B.; Jarosz, S. Chem. Commun. 2008, 6399–6401.
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The support from Grant: POIG.01.01.02-14-102/09 (part-fi-
nanced by the European Union within the European Regional
Development Fund) is acknowledged.
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