An efficient synthesis of novel sucrose-containing dilactams

Article abstract of DOI:10.1007/s00706-012-0894-2

An efficient and convenient approach to sucrose-containing dilactams has been developed. The method, based on reaction of regioisomeric 6,6′-di-O-[(aminomethyl)-phenyl]-1′,2,3,3′,4, 4′-hexa-O-methylsucrose with isophtaloyl or 2,6-pyridinedicarbonyl dichlo

Full text of DOI:10.1007/s00706-012-0894-2

Monatsh Chem (2013) 144:437–443
DOI 10.1007/s00706-012-0894-2
ORIGINAL PAPER
An efficient synthesis of novel sucrose-containing dilactams
•
Mykhaylo A. Potopnyk Sławomir Jarosz
Received: 27 September 2012 / Accepted: 29 November 2012 / Published online: 17 January 2013
Ó The Author(s) 2013. This article is published with open access at Springerlink.com
Abstract An efficient and convenient approach to sucrose-
containing dilactams has been developed. The method, based
on reaction of regioisomeric 6,60-di-O-[(aminomethyl)-
phenyl]-10,2,3,30,4,40-hexa-O-methylsucrose with isophtaloyl
or 2,6-pyridinedicarbonyl dichlorides, provided the 1:1-mac-
rocycles in good yields.
been investigated as fluorescent molecular sensors for
cations [9, 10] and anions [11].
Sucrose, the most common disaccharide occurring in
nature, is a promising building block for synthesis of such
chiral macrocyclic receptors [12–14]. Its aza-crown
derivatives enabled highly enantioselective complexation
of the (S)-1-phenylethylammonium cation [15].
Keywords Carbohydrates ꢀ Macrocycles ꢀ Alkylation ꢀ
Reductions ꢀ Cyclization
Isophthalic and pyridine-2,6-diamides, because of their
proton-donor properties, are convenient scaffolds used as
building blocks in the synthesis of macrocyclic receptors
designed for complexation of anions [16], ion pairs [17],
zwitterions [18], and amino acid derivatives [19]. The
anion-complexing properties of such diamides have been
exploited in templated syntheses of catenane [20] and
rotaxane [21] systems. Macrocycles incorporating the
pyridine-2,6-diamide functionality are known as molecular
turnstiles [22]. Combination of the sucrose scaffold with
isophthalic or pyridine-2,6-diamide units may be useful
means of synthesis of a new type of chiral receptor with
interesting properties.
Introduction
Macrocyclic compounds are important in supramolecular
chemistry [1]. Especially interesting are chiral receptors
capable of enantioselective complexation of a variety of
important chiral guests. Carbohydrates, inexpensive,
renewable raw materials available optically pure, are par-
ticularly useful in planning and executing the synthesis of
such chiral hosts. The different configurations and con-
formations of carbohydrates can be incorporated in the
target macrocycle, which makes these compounds conve-
nient chiral synthetic analogs of poly(ethylene glycol)
(PEG) reagents [2].
Very recently, we reported an effective procedure for
synthesis of 10,2,3,30,4,40-hexa-O-methyl-6,60-di-O-(meth-
ylsulfonyl)sucrose (1; four steps, 48 % overall yield)
which was used for preparation of macrocyclic bis-amides
3a–3c and 4a–4c (Scheme 1). Condensation of dimesylate
1 with 2 equiv. of the appropriate nitrophenol (ortho, meta,
or para) followed by reduction of the nitro groups provided
the expected 6,60-di-O-(aminophenyl)-10,2,3,30,4,40-hexa-
O-methylsucroses (2a–2c). Reaction of dianilines 2a
and 2b (o or m) with isophthaloyl or 2,6-pyridinedicar-
bonyl dichlorides (5 and 6) afforded the monomeric
macrocycles in excellent yields, whereas reaction of the
p-diamines furnished dimers as the major products
(Scheme 1), with smaller amounts of the expected mono-
mers 3c, 4c [23].
Chiral crown and aza-crown ethers with carbohydrate
scaffolds have been extensively used as chiral catalysts in
asymmetric synthesis (asymmetric epoxidation of chalcones
[3–5], Michael addition [3, 4, 6, 7], and Darzens reactions
[3–5, 7, 8]). Carbohydrate-containing macrocycles have also
M. A. Potopnyk ꢀ S. Jarosz (&)
Institute of Organic Chemistry, Polish Academy of Sciences,
Kasprzaka 44/52, 01-224 Warsaw, Poland
e-mail: slawomir.jarosz@icho.edu.pl
123

438
M. A. Potopnyk, S. Jarosz
Sucrose
4 steps
NH2
O
O
H2N
X
(48% overall)
O
O
NH
HN
O
1. Nitrophenol,
K2CO3
2. Hydrogenation
X
Cl
Cl
O
OMs
O
O
MsO
5, 6
dimers
+
OMe
OMe
MeO
MeO
O
O
Et3N
MeO
MeO
O
O
O
(for para)
OMe
OMe
O
OMe
MeO
MeO
O
O
OMe
OMe
OMe
OMe
OMe
O
1
2a: o-NH2
2b: m-NH2
2c: p-NH2
3, 5: X = CH,
4, 6: X = N
OMe
OMe
3a-3c, 4a-4c
Scheme 1
A crucial aspect of the synthesis of this type of receptor
is the relative orientation of the two amino groups in the
energetically accessible conformations of the substrates.
The amino groups in the p-substituted derivative 2c are
rather distant from each other (compared with the o and
m analogs 2a and 2b). Thus, the intermediate formed in
reaction of the acid dichloride (5 or 6) with the first amino
group will react preferentially with a second molecule of 2c
(to form the dimer) rather than undergo the intramolecular
process leading to 3c or 4c [23].
mobility (less rigid structure) of the diamine 9c, which differ
from 2c (which furnishes both the monomers and the dimers
in the reaction with dichlorides 5 or 6; Scheme 1) only in the
length of the chain, we were able to suppress formation of the
dimer and obtain monomeric macrocycles in good yield. This
strategy was applicable to the synthesis of sucrose-derived
macrocycles containing isophthalic and pyridine-2,6-diamide
groups.
Experimental
Results and Discussion
All reported NMR spectra were recorded with a Varian
Vnmrs-600 MHz spectrometer (at 600 and 150 MHz for
1H and 13C NMR spectra, respectively); solutions were
prepared in CDCl3 with TMS as the internal standard. Most
of the resonances were assigned by COSY (1H–1H) and
gradient selected HSQC and HMBC correlations. IR
spectra (CHCl3, film) were recorded on a Perkin Elmer FT-
IR Spectrum 2000. Mass spectra were recorded with an
ESI/MS Mariner (PerSeptive Biosystem) mass spectrome-
ter. Elemental analysis was performed with a Perkin-Elmer
2400 CHN analyzer; results agreed satisfactorily with
calculated values. Optical rotation was measured with a
Jasco DIP-360 digital polarimeter; solutions were prepared
in CH2Cl2 (c = 1). Flash chromatography was performed
on silica gel (Merck, 230–400 mesh). The organic phases
were dried over anhydrous magnesium sulfate.
In this paper we report the synthesis of new sucrose
macrocyclic derivatives which are twice homologated
compared with compounds 3a–3c and 4a–4c. Arylme-
thaneamines 9a–9c (the homologated analogs of anilines
2a–2c) were used as starting materials for the preparation
of conformationally less demanding structures.
10,2,3,30,4,40-Hexa-O-methyl-6,60-di-O-(methylsulfo-
nyl)sucrose (1) was treated with 2 equiv. of the appropriate,
commercially available cyanophenol (7a–7c; o, m, p,
respectively) in DMF in the presence of potassium car-
bonate to give the corresponding 6,60-di-O-(cyanophenyl)-
10,2,3,30,4,40-hexa-O-methylsucroses (8a–8c) in 81–84 %
yield. These compounds were quantitatively converted into
the 6,60-di-O-[(aminomethyl)phenyl]-10,2,3,30,4,40-hexa-O-
methylsucroses (9a–9c) by reduction with LiAlH4. The
crude bis-amines 9a–9c were subjected to cyclocondensa-
tion reaction with isophthaloyl or 2,6-pyridinedicarbonyl
dichlorides (5 and 6, respectively) to achieve closure of the
ring (Scheme 2). To avoid formation of the dimeric
byproducts, the reactions were performed in dilute solu-
tion. In all cases a 1:1-product (10a–10c and 11a–11c) was
formed in good yield (63–74 %; Fig. 1).
General procedure for preparation of 6,60-di-O-
(cyanophenyl)-10,2,3,30,4,40-hexa-O-methylsucroses
(8a–8c)
To a solution of 291 mg compound 1 (0.5 mmol) in 25 cm3
dry DMF, 345 mg K2CO3 (2.5 mmol) was added than
179 mg of the corresponding cyanophenol 7a–7c (1.5 mmol).
The mixture was stirred for 24 h at 100 °C then cooled to
room temperature. Water (50 cm3) and 50 cm3 AcOEt were
added, the organic phase was separated, and the aqueous
In summary, we have developed a simple, rapid, and
efficient procedure for preparation of sucrose-based promis-
ing optically active receptors. Because of the conformational
123

Synthesis of dilactams
439
Scheme 2
CN
CN
O
O
a
NC
1
+
OMe
MeO
MeO
OH
7a-7c
O
O
OMe
O
OMe
OMe
8a-8c
b
O
O
X
H2N
NH2
NH
O
HN
O
O
O
c
OMe
O
OMe
O
MeO
MeO
MeO
MeO
O
O
OMe
OMe
O
O
OMe
OMe
OMe
OMe
10a-10c: X = CH
11a-11c: X = N
9a-9c
(a) K2CO3, DMF, 100 °C, 24 h; (b) LiAlH4, THF, 60 °C, 1 h; (c) 5 or 6,
Et3N, CH2Cl2, rt, 1 h
O
O
O
O
O
X
X
O
O
X
HN
NH
NH
HN
O
NH
NH
O
O
O
O
O
O
OMe
O
MeO
MeO
OMe
O
OMe
O
MeO
MeO
MeO
MeO
OMe
O
O
OMe
OMe
OMe
O
OMe
O
OMe
OMe
OMe
OMe
10a: X = CH (64%)
11a: X = N (67%)
10c: X = CH (71%)
11c: X = N (74%)
10b: X = CH (63%)
11b: X = N (66%)
Fig. 1 Macrocyclic diamides 10a–10c and 11a–11c
phase was extracted with ethyl acetate (4 9 50 cm3).
Combined organic solutions were washed with water
(2 9 30 cm3), 30 cm3 brine, dried, concentrated, and the
product was isolated by flash chromatography (hexane–ethyl
acetate, 9:1 to 7:3) to afford 8a–8c.
6,60-Di-O-(2-cyanophenyl)-10,2,3,30,4,40-hexa-O-
methylsucrose (8a, C32H40N2O11)
Colorless oil; yield: 255 mg (81 %); TLC: Rf = 0.47 (hex-
ane/AcOEt 1:2); [a]2D4 = ?55.9° cm2 g-1; IR: v = 2,983,
2,934, 2,832, 2,228, 1,741, 1,599, 1,581, 1,494, 1,449, 1,374,
123

440
M. A. Potopnyk, S. Jarosz
1,292, 1,261, 1,185, 1,164, 1,102, 1,045, 1,018, 983, 879,
835, 757, 667, 566, 497 cm-1
6,60-Di-O-(4-cyanophenyl)-10,2,3,30,4,40-hexa-O-
methylsucrose (8c, C32H40N2O11)
;
1H NMR: d = 7.55 (dd,
J = 7.7 Hz, 1.7 Hz, 1H, Ar), 7.53 (dd, J = 7.5 Hz, 1.7 Hz,
1H, Ar), 7.51 (ddd, J = 8.4 Hz, 7.6 Hz, 1.6 Hz, 1H, Ar),
7.37 (ddd, J = 8.5 Hz, 7.6 Hz, 1.7 Hz, 1H, Ar), 6.99–7.07
(m, 3H, Ar), 6.95 (dd, J = 7.6 Hz, 7.6 Hz, 1H, Ar), 5.59 (d,
J1,2 = 3.7 Hz, 1H, H-1), 4.32–4.38 (m, 2H, 2H-60), 4.23–
4.27 (m, 3H, H-50, 2H-6), 4.18 (m, 1H, H-5), 4.09
Colorless oil; yield: 258 mg (82 %); TLC: Rf = 0.54
;
(hexane/AcOEt 1:2); [a]2D4 = ?75.8° cm2 g-1
v = 2,983, 2,933, 2,831, 2,225, 1,606, 1,575, 1,509,
IR:
1,453, 1,419, 1,374, 1,302, 1,259, 1,173, 1,150, 1,100,
1,019, 983, 836, 755, 724, 684, 548 cm-1 1H NMR:
;
d = 7.59 (d, J = 9.0 Hz, 2H, Ar), 7.50 (d, J = 9.0 Hz, 2H,
Ar), 6.98 (d, J = 9.0 Hz, 2H, Ar), 6.94 (d, J = 9.0 Hz, 2H,
Ar), 5.60 (d, J1,2 = 3.7 Hz, 1H, H-1), 4.32 (m, 1H, H-60),
4.14–4.22 (m, 5H, H-5, 2H-6, H-50, H-60), 4.10 (d,
(d, J3 ,4 = 6.7 Hz, 1H, H-30), 3.90 (dd, J4 ,3 = 6.7 Hz,
0
0
0
0
J4 ,5 = 6.1 Hz, 1H, H-40), 3.66 (d, J1 ,1 = 11.1 Hz, 1H, H-
10), 3.60 (s, 3H, CH3), 3.54 (s, 3H, CH3), 3.51 (dd,
J3,2 = 9.7 Hz, J3,4 = 9.1 Hz, 1H, H-3), 3.49 (s, 3H, CH3),
3.47 (s, 3H, CH3), 3.46 (s, 3H, CH3), 3.43 (d,
0
0
0
0
J3 ,4 = 7.5 Hz, 1H, H-30), 3.93 (dd, J4 ,3 = 7.5 Hz,
0
0
0
0
J4 ,5 = 7.3 Hz, 1H, H-40), 3.62 (s, 3H, CH3), 3.61 (d,
0
0
J1 ,1 = 11.1 Hz, 1H, H-10), 3.42 (s, 3H, CH3), 3.34 (dd,
J4,3 = 9.1 Hz, J4,5 = 10.0 Hz, 1H, H-4), 3.16 (dd,
J2,1 = 3.7 Hz, J2,3 = 9.7 Hz, 1H, H-2) ppm; 13C NMR:
d = 160.49, 160.33, 134.33, 134.15, 133.82, 133.82, 121.13,
121.01, 116.40, 116.30, 112.87, 112.79 (12 9 C–Ar), 104.98
(C-20), 102.33 (CN), 102.25 (CN), 90.02 (C-1), 85.88 (C-30),
84.92 (C-40), 83.12 (C-3), 81.46 (C-2), 79.16 (C-4), 78.83
(C-50), 73.30 (C-10), 70.42 (C-60), 69.71 (C-5), 68.52 (C-6),
60.63, 60.47, 59.51, 58.75, 58.55, 58.46 (6 9 OCH3) ppm;
HRMS (ESI): calcd for C32H40N2O11Na [M ? Na]?
651.2524, found 651.2525.
J1 ,1 = 10.8 Hz, 1H, H-10), 3.52 (s, 3H, CH3), 3.49 (s, 3H,
CH3), 3.49 (dd, J3,2 = 9.7 Hz, J3,4 = 8.9 Hz, 1H, H-3),
3.435 (s, 3H, CH3), 3.432 (s, 3H, CH3), 3.427 (d,
0
0
0
0
J1 ,1 = 10.8 Hz, 1H, H-10), 3.418 (s, 3H, CH3), 3.20 (dd,
J4,3 = 8.9 Hz, J4,5 = 9.7 Hz, 1H, H-4), 3.15 (dd,
J2,1 = 3.7 Hz, J2,3 = 9.7 Hz, 1H, H-2) ppm; 13C NMR:
d = 161.92, 161.89, 134.11, 133.93, 119.03, 118.94,
115.33, 115.27 (12 9 C–Ar), 104.54 (CN), 104.50 (C-20),
104.36 (CN), 89.46 (C-1), 85.35 (C-30), 83.64 (C-40), 83.24
(C-3), 81.70 (C-2), 79.47 (C-4), 78.49 (C-50), 73.68 (C-10),
69.51 (C-5), 69.33 (C-60), 67.78 (C-6), 60.78, 60.63, 59.46,
58.72, 58.51, 58.39 (6 9 OCH3) ppm; HRMS (ESI):
calcd for C32H40N2O11Na [M ? Na]? 651.2524, found
651.2538.
0
0
6,60-Di-O-(3-cyanophenyl)-10,2,3,30,4,40-hexa-O-
methylsucrose (8b, C32H40N2O11)
Colorless oil; yield: 265 mg (84 %); TLC: Rf = 0.51
(hexane/AcOEt 1:2); [a]2D2 = ?56.3° cm2 g-1
v = 3,075, 2,982, 2,933, 2,831, 2,231, 1,741, 1,597,
1,579, 1,483, 1,432, 1,328, 1,291, 1,265, 1,185, 1,148,
1,101, 1,017, 983, 873, 790, 756, 682, 616, 517, 475 cm-1
General procedure for synthesis of 6,60-di-O-
[4-(aminomethyl)phenyl]-10,2,3,30,4,40-hexa-O-
methylsucroses (9a–9c)
;
IR:
;
1H NMR: d = 7.36 (dd, J = 7.8 Hz, 8.0 Hz, 1H, Ar), 7.28
(dd, J = 7.8 Hz, 8.2 Hz, 1H, Ar), 7.24 (d, J = 7.6 Hz, 1H,
Ar), 7.20 (d, J = 7.4 Hz, 1H, Ar), 7.12–7.17 (m, 3H, Ar),
7.11 (dd, J = 8.2 Hz, 2.3 Hz, 1H, Ar), 5.60 (d,
J1,2 = 3.7 Hz, 1H, H-1), 4.29 (m, 1H, H-60), 4.12–4.23
To a cooled (0 °C) solution of 215 mg compound 8a–8c
(0.34 mmol) in 30 cm3 dry THF, 93 mg LiAlH4
(2.45 mmol) was added slowly within 5 min. The mixture
was stirred for 1 h at 60 °C and cooled to room tempera-
ture. Excess hydride was carefully decomposed with
10 cm3 water and 40 cm3 aqueous potassium bisulfate
(KHSO4). Ethyl acetate (50 cm3) was added, the layers
were separated, and the aqueous layer was extracted with
ethyl acetate (3 9 40 cm3). The combined organic solu-
tions were dried, concentrated, and the crude product was
used in the next step without purification.
(m, 5H, H-5, H-50, 2H-6, H-60), 4.11 (d, J3 ,4 = 7.6 Hz,
0
0
1H, H-30), 3.97 (dd, J4 ,3 = 7.6 Hz, J4 ,5 = 7.3 Hz, 1H, H-
0
0
0
0
40), 3.64 (s, 3H, CH3), 3.61 (d, J1 ,1 = 11.0 Hz, 1H, H-10),
3.53 (s, 3H, CH3), 3.51 (s, 3H, CH3), 3.49 (m, 1H, H-3),
3.47 (s, 3H, CH3), 3.44 (s, 3H, CH3), 3.43 (s, 3H, CH3),
0
0
3.43 (d, J1 ,1 = 11.0 Hz, 1H, H-10), 3.22 (dd, J = 10.2 Hz,
8.9 Hz, 1H, H-4), 3.16 (dd, J2,1 = 3.7 Hz, J2,3 = 9.7 Hz,
1H, H-2) ppm; 13C NMR: d = 158.74, 158.65, 130.47,
130.26, 124.83, 124.76, 119.90, 119.84, 118.51, 118.51,
117.48, 117.39 (12 9 C–Ar), 113.30 (CN), 113.16 (CN),
104.39 (C-20), 89.39 (C-1), 85.34 (C-30), 83.79 (C-40),
83.21 (C-3), 81.64 (C-2), 79.47 (C-4), 78.53 (C-50), 73.70
(C-10), 69.66 (C-5), 69.30 (C-60), 67.80 (C-6), 60.76, 60.58,
59.42, 58.65, 58.47, 58.43 (6 9 OCH3) ppm; HRMS (ESI):
calcd for C32H40N2O11Na [M ? Na]? 651.2524, found
651.2522.
0
0
General procedure for syntheses of macrocyclic
diamides 10a–10c and 11a–11c
This reaction was conducted under an argon atmosphere:
35 mg isophthaloyl or 2,6-pyridinedicarbonyl dichloride (5
or 6, 0.17 mmol) was dissolved in 20 cm3 dry CH2Cl2 and
added dropwise to a stirred solution of 108 mg diamine
9a–9c (0.17 mmol) in 40 cm3 dry CH2Cl2 containing
71 mm3 Et3N (0.51 mmol), and the mixture was stirred for
123

Synthesis of dilactams
441
1,735, 1,674, 1,602, 1,590, 1,528, 1,494, 1,452, 1,360,
1,289, 1,278, 1,244, 1,186, 1,161, 1,149, 1,101, 1,051,
1,017, 1,003, 983, 945, 878, 844, 754, 683, 647, 609,
1 h at room temperature. The resulting solution was con-
centrated in vacuum and the residue was dissolved in
40 cm3 ethyl acetate and 20 cm3 water. Saturated K2CO3
solution (10 cm3) was added, the layers were separated,
and the aqueous layer was extracted with ethyl acetate
(3 9 30 cm3). The combined organic extracts were washed
with 20 cm3 water and 10 cm3 brine, dried, concentrated,
and the products were isolated by flash chromatography
(hexane–ethyl acetate, 50:50 to 25:75).
1
564 cm-1; H NMR: d = 8.48 (dd, J = 4.3 Hz, 7.3 Hz,
1H, NH), 8.34–8.37 (m, 2H, pyridine), 8.22 (dd,
J = 4.1 Hz, 7.6 Hz, 1H, NH), 8.02 (t, J = 7.8 Hz, 1H,
pyridine), 7.39 (dd, J = 7.5 Hz, 1.6 Hz, 1H, Ar), 7.30 (dd,
J = 7.6 Hz, 1.6 Hz, 1H, Ar), 7.23–7.29 (m, 2H, Ar), 6.99
(dd, J = 8.2 Hz, 0.8 Hz, 1H, Ar), 6.93 (ddd, J = 7.5 Hz,
7.4 Hz, 0.9 Hz, 1H, Ar), 6.88 (ddd, J = 7.6 Hz, 7.4 Hz,
0.8 Hz, 1H, Ar), 6.99 (dd, J = 8.2 Hz, 0.9 Hz, 1H, Ar),
5.35 (d, J1,2 = 3.4 Hz, 1H, H-1), 4.85 (dd, J = 14.4 Hz,
4.3 Hz, 1H, CH2N), 4.78 (dd, J = 14.2 Hz, 4.1 Hz, 1H,
CH2N), 4.69 (dd, J = 14.4 Hz, 7.3 Hz, 1H, CH2N), 4.61
(dd, J = 14.2 Hz, 7.6 Hz, 1H, CH2N), 4.34 (dd,
6,60-Di-O-[[benzene-1,3-diyl-bis(carbonylaminomethyl)]-
2,20-diphenyl]-10,2,3,30,4,40-hexa-O-methylsucrose
(10a, C40H50N2O13)
White solid; yield: 84 mg (64 %); m.p.: 134 °C; TLC:
Rf = 0.35
(AcOEt);
[a]2D2 = ?78.8° cm2 g-1
;
IR:
v = 3,347, 3,064, 2,982, 2,933, 2,830, 1,658, 1,603,
1,590, 1,526, 1,495, 1,451, 1,359, 1,318, 1,293, 1,250,
1,186, 1,161, 1,100, 1,049, 1,017, 1,004, 982, 941, 882,
J6 ,6 = 10.2 Hz, J6 ,5 = 3.1 Hz, 1H, H-60), 4.22 (m, 1H,
0
0
0
0
H-50), 4.11 (d, J3 ,4 = 6.9 Hz, 1H, H-30), 4.01–4.07 (m,
0
0
0
0
0
0
2H, H-5, H-6), 3.98 (dd, J6 ,5 = 7.7 Hz, J6 ,6 = 10.2 Hz,
0
1
825, 753, 710, 593, 527 cm-1; H NMR: d = 8.01–8.05
1H, H-60), 3.86 (dd, J4 ,3 = 6.9 Hz, J4 ,5 = 6.9 Hz, 1H, H-
40), 3.76 (d, J6,6 = 9.2 Hz, 1H, H-6), 3.57 (d,
0
0
0
(m, 2H, isophthalic), 7.57 (s, 1H, isophthalic), 7.52 (t,
J = 7.7 Hz, 1H, isophthalic), 7.32 (d, J = 7.3 Hz, 1H, Ar),
7.26–7.31 (m, 3H, Ar), 6.92–6.96 (m, 2H, Ar), 6.90
(d, J = 8.5 Hz, 1H, Ar), 6.85 (br s, 1H, NH), 6.74
(d, J = 8.0 Hz, 1H, Ar), 6.66 (br s, 1H, NH), 4.72–4.77
(m, 2H, CH2N), 4.59 (d, J1,2 = 3.3 Hz, 1H, H-1), 4.51 (dd,
J = 13.8 Hz, 6.2 Hz, 1H, CH2N), 4.45 (dd, J = 13.6 Hz,
J1 ,1 = 11.0 Hz, 1H, H-10), 3.52 (s, 3H, CH3), 3.48 (dd,
J3,2 = 9.6 Hz, J3,4 = 9.0 Hz, 1H, H-3), 3.460 (s, 3H,
CH3), 3.457 (s, 3H, CH3), 3.450 (s, 3H, CH3), 3.42 (s, 3H,
0
0
CH3), 3.41 (d, J1 ,1 = 11.0 Hz, 1H, H-10), 3.32 (dd,
J4,3 = 9.0 Hz, J4,5 = 9.6 Hz, 1H, H-4), 3.25 (s, 3H,
CH3), 2.81 (dd, J2,1 = 3.4 Hz, J2,3 = 9.6 Hz, 1H, H-2)
ppm; 13C NMR: d = 163.38 (C=O), 163.12 (C=O), 156.67,
156.64 (2 9 C–Ar), 148.98, 148.89, 138.83 (3 9 C-pyri-
dine), 130.72, 130.02, 129.03, 128.71, 128.34, 126.42
(6 9 C–Ar), 124.74, 124.74 (2 9 C-pyridine), 122.67,
121.43, 114.94, 112.44 (4 9 C–Ar), 104.92 (C-20), 89.89
(C-1), 84.85 (C-30), 84.19 (C-40), 82.81 (C-3), 81.88 (C-2),
79.03 (C-4), 78.69 (C-50), 73.65 (C-10), 72.06 (C-60), 70.26
(C-5), 67.30 (C-6), 60.48, 60.42, 59.54, 58.50, 58.38, 58.03
(6 9 OCH3), 39.65, 38.14 (2 9 CH2N) ppm; HRMS
(ESI): calcd for C39H49N3O13Na [M ? Na]? 790.3158,
found 790.3165.
0
0
0
0
0
0
=
6.5 Hz, 1H, CH2N), 4.27 (dd, J6 ,6 = 9.9 Hz, J6 ,5
2.3 Hz, 1H, H-60), 4.14–4.20 (m, 2H, H-50, H-6), 4.08 (d,
J3 ,4 = 7.4 Hz, 1H, H-30), 3.93–3.97 (m, 2H, H-5, H-60),
3.76 (dd, J6,6 = 10.0 Hz, J6,5 = 1.5 Hz, 1H, H-6), 3.70
0
0
(dd, J4 ,5 = 7.5 Hz, J4 ,3 = 7.4 Hz, 1H, H-40), 3.56 (s, 3H,
CH3), 3.47 (s, 3H, CH3), 3.46 (m, 1H, H-3), 3.440 (s, 3H,
CH3), 3.435 (s, 3H, CH3), 3.40–3.43 (m, 2H, H-10, H-4),
0
0
0
0
0
0
=
3.39 (s, 3H, CH3), 3.23 (s, 3H, CH3), 3.14 (d, J1 ,1
11.2 Hz, 1H, H-10), 2.75 (dd, J2,1 = 3.3 Hz, J2,3 = 9.5 Hz,
1H, H-2) ppm; 13C NMR: d = 166.96 (C=O), 166.75
(C=O), 156.85, 156.81 (2 9 C–Ar), 135.53, 135.42,
131.21, 130.87 (4 9 C-isophthalic), 131.09, 130.84,
129.43, 129.31 (4 9 C–Ar), 129.16 (C-isophthalic),
127.05, 125.73 (2 9 C–Ar), 123.80 (C-isophthalic),
121.72, 121.10, 112.51, 110.99 (4 9 C–Ar), 104.37 (C-
20), 90.41 (C-1), 84.70 (C-30), 84.09 (C-40), 82.72 (C-3),
81.31 (C-2), 78.59 (C-4), 77.87 (C-50), 73.53 (C-10), 70.95
(C-60), 70.25 (C-5), 66.07 (C-6), 60.67, 60.33, 59.67, 58.87,
58.04, 57.99 (6 9 OCH3), 41.53, 40.94 (2 9 CH2N) ppm;
HRMS (ESI): calcd for C40H50N2O13Na [M ? Na]?
789.3205, found 789.3228.
6,60-Di-O-[[benzene-1,3-diyl-bis(carbonylaminomethyl)]-
3,30-diphenyl]-10,2,3,30,4,40-hexa-O-methylsucrose
(10b, C40H50N2O13)
White solid; yield: 82 mg (63 %); m.p.: 111 °C; TLC:
Rf = 0.36
(AcOEt);
[a]2D2 = ?59.8° cm2 g-1
;
IR:
v = 3,333, 2,981, 2,931, 2,830, 1,654, 1,599, 1,586,
1,535, 1,487, 1,448, 1,358, 1,290, 1,267, 1,237, 1,183,
1,151, 1,100, 1,056, 1,017, 997, 983, 956, 876, 755, 691,
1
622 cm-1; H NMR: d = 7.97–8.01 (m, 2H, isophthalic),
6,60-Di-O-[[pyridine-1,3-diyl-bis(carbonylaminomethyl)]-
2,20-diphenyl]-10,2,3,30,4,40-hexa-O-methylsucrose
(11a, C39H49N3O13)
7.91 (s, 1H, isophthalic), 7.52 (dd, J = 7.8 Hz, 7.8 Hz, 1H,
isophthalic), 7.24 (dd, J = 7.8 Hz, 7.9 Hz, 1H, Ar), 7.19
(dd, J = 7.8 Hz, 8.0 Hz, 1H, Ar), 6.97 (s, 1H, Ar), 6.91 (d,
J = 7.8 Hz, 1H, Ar), 6.87–6.89 (m, 2H, Ar), 6.82–6.86 (m,
2H, Ar), 6.69 (dd, J = 5.6 Hz, 5.6 Hz, 1H, NH), 6.64 (dd,
J = 5.6 Hz, 5.6 Hz, 1H, NH), 5.70 (d, J1,2 = 3.8 Hz, 1H,
White solid; yield: 88 mg (67 %); m.p.: 96 °C; TLC:
Rf = 0.37 (AcOEt); [a]2D2 = ?163.1° cm2 g-1
v = 3,537, 3,403, 3,303, 3,064, 2,984, 2,933, 2,831,
;
IR:
123

442
M. A. Potopnyk, S. Jarosz
H-1), 4.65 (m, 2H, CH2N), 4.50 (dd, J = 14.7 Hz, 5.6 Hz,
1H, CH2N), 4.42 (dd, J = 14.5 Hz, 5.6 Hz, 1H, CH2N),
4.12–4.23 (m, 4H, H-5, H-6, 2 9 H-60), 4.06–4.12 (m, 1H,
NMR: d = 163.14 (C=O), 163.08 (C=O), 159.16, 158.93
(2 9 C–Ar), 148.63, 148.54 (2 9 C-pyridine), 139.25,
139.13 (2 9 C–Ar), 139.13 (C-pyridine), 129.96, 129.92
(2 9 C–Ar), 125.17, 125.14 (2 9 C-pyridine), 121.11,
120.84, 114.41, 114.17, 113.74, 112.95 (6 9 C–Ar),
104.07 (C-20), 89.93 (C-1), 84.93 (C-30), 83.61 (C-40),
83.23 (C-3), 81.51 (C-2), 79.45 (C-4), 78.37 (C-50), 74.19
(C-10), 69.70 (C-5), 69.23 (C-60), 66.77 (C-6), 60.69, 60.47,
59.34, 58.53, 58.41, 58.22 (6 9 OCH3), 43.66, 43.63
(2 9 CH2N) ppm; HRMS (ESI): calcd for C39H49N3O13Na
[M ? Na]? 790.3158, found 790.3125.
H-50), 4.09 (d, J3 ,4 = 8.0 Hz, 1H, H-30), 4.03 (br d,
0
0
0
J6,6 = 9.1 Hz, 1H, H-6), 3.97 (dd, J4 ,3 = 8.0 Hz,
0
J4 ,5 = 8.0 Hz, 1H, H-40), 3.61 (s, 3H, CH3), 3.58 (d,
0
0
J1 ,1 = 10.9 Hz, 1H, H-10), 3.49 (s, 3H, CH3), 3.48 (dd,
J3,2 = 9.6 Hz, J3,4 = 9.3 Hz, 1H, H-3), 3.45 (s, 3H, CH3),
0
0
3.42 (d, J1 ,1 = 10.9 Hz, 1H, H-10), 3.41 (s, 6H, 2CH3),
3.40 (s, 3H, CH3), 3.36 (dd, J4,3 = 9.3 Hz, J4,5 = 9.6 Hz,
1H, H-4), 3.21 (dd, J2,1 = 3.8 Hz, J2,3 = 9.6 Hz, 1H, H-2)
ppm; 13C NMR: d = 166.71 (C=O), 166.34 (C=O), 159.20,
159.01, 139.63, 139.28 (4 9 C–Ar), 134.69, 134.56
(2 9 C-isophthalic), 130.78 (2C-isophthalic), 129.79,
129.77 (2 9 C–Ar), 129.39, 124.05 (2 9 C-isophthalic),
121.64, 120.80, 115.13, 114.48, 113.75, 112.49
(6 9 C–Ar), 104.15 (C-20), 88.69 (C-1), 85.02 (C-30),
83.17 (C-3), 83.03 (C-40), 81.29 (C-2), 79.14 (C-4), 78.08
(C-50), 74.83 (C-10), 69.66 (C-5), 68.95 (C-60), 66.30 (C-6),
60.65, 60.46, 59.41, 58.59, 58.39, 58.03 (6 9 OCH3),
44.25, 43.95 (2 9 CH2N) ppm; HRMS (ESI): calcd for
C40H50N2O13Na [M ? Na]? 789.3202, found 789.3214.
0
0
6,60-Di-O-[[benzene-1,3-diyl-bis(carbonylaminomethyl)]-
4,40-diphenyl]-10,2,3,30,4,40-hexa-O-methylsucrose
(10c, C40H50N2O13)
White solid; yield: 93 mg (71 %); m.p.: 144 °C; TLC:
Rf = 0.35
(AcOEt);
[a]2D4 = ?58.2° cm2 g-1
;
IR:
v = 3,301, 3,064, 2,982, 2,931, 2,831, 1,649, 1,613,
1,586, 1,542, 1,514, 1,455, 1,422, 1,359, 1,319, 1,300,
1,248, 1,160, 1,101, 1,024, 983, 951, 824, 754, 700, 603,
580 cm-1
;
1H NMR: d = 7.88 (d, J = 7.8 Hz, 1H,
isophthalic), 7.85 (d, J = 7.6 Hz, 1H, isophthalic), 7.56
(s, 1H, isophthalic), 7.45 (dd, J = 7.8 Hz, 7.6 Hz, 1H,
isophthalic), 7.22 (d, J = 8.5 Hz, 2H, Ar), 7.07 (d,
J = 8.5 Hz, 2H, Ar), 6.91 (d, J = 8.5 Hz, 2H, Ar), 6.78
(d, J = 8.5 Hz, 2H, Ar), 6.61 (br s, 1H, NH), 6.56 (br s,
1H, NH), 5.55 (d, J1,2 = 3.7 Hz, 1H, H-1), 4.45 (dd,
J = 13.9 Hz, 5.2 Hz, 1H, CH2N), 4.39 (dd, J = 13.8 Hz,
6.7 Hz, 1H, CH2N), 4.35–4.39 (m, 2H, H-60, CH2N), 4.32
(dd, J = 13.8 Hz, 4.8 Hz, 1H, CH2N), 4.28 (m, 1H, H-5),
6,60-Di-O-[[pyridine-1,3-diyl-bis(carbonylaminomethyl)]-
3,30-diphenyl]-10,2,3,30,4,40-hexa-O-methylsucrose
(11b, C39H49N3O13)
White solid; yield: 86 mg (66 %); m.p.: 125 °C; TLC:
Rf = 0.39
(AcOEt);
[a]2D2 = ?61.6° cm2 g-1
;
IR:
v = 3,317, 2,980, 2,930, 2,831, 1,679, 1,661, 1,599,
1,586, 1,532, 1,488, 1,448, 1,358, 1,312, 1,287, 1,271,
1,237, 1,180, 1,148, 1,101, 1,057, 1,038, 1,019, 1,002, 982,
0
0
0
0
0
0
4.20 (ddd, J5 ,4 = 8.3 Hz, J5 ,6 = 6.7 Hz, J5 ,6 = 3.3 Hz,
0
1
876, 844, 755, 682, 647, 623 cm-1; H NMR: d = 8.34–
1H, H-50), 4.14 (d, J3 ,4 = 7.9 Hz, 1H, H-30), 4.13 (m, 1H,
H-6), 4.09 (dd, J6,6 = 9.8 Hz, J6,5 = 5.3 Hz, 1H, H-6),
4.05 (dd, J6 ,6 = 9.9 Hz, J6 ,5 = 3.3 Hz, 1H, H-60), 4.03
(dd, J4 ,3 = 7.9 Hz, J4 ,5 = 8.3 Hz, 1H, H-40), 3.65 (s, 3H,
0
8.38 (m, 2H, pyridine), 8.04 (t, J = 7.8 Hz, 1H, pyridine),
7.90 (dd, J = 5.1 Hz, 6.6 Hz, 1H, NH), 7.85 (dd,
J = 5.6 Hz, 5.6 Hz, 1H, NH), 7.25 (dd, J = 7.5 Hz,
7.9 Hz, 1H, Ar), 7.10 (dd, J = 7.9 Hz, 7.9 Hz, 1H, Ar),
6.92 (d, J = 7.5 Hz, 1H, Ar), 6.91 (d, J = 7.9 Hz, 1H, Ar),
6.81–6.89 (m, 4H, Ar), 5.59 (d, J1,2 = 3.7 Hz, 1H, H-1),
4.70 (dd, J = 14.7 Hz, 6.6 Hz, 1H, CH2N), 4.61 (dd,
J = 14.7 Hz, 5.6 Hz, 1H, CH2N), 4.58 (dd, J = 14.7 Hz,
5.6 Hz, 1H, CH2N), 4.44 (dd, J = 14.7 Hz, 5.1 Hz, 1H,
CH2N), 4.27 (m, 1H, H-60), 4.21 (ddd, J5,4 = 10.1 Hz,
J5,6 = 3.9 Hz, J5,6 = 1.6 Hz, 1H, H-5), 4.10–4.17 (m, 3H,
0
0
0
0
0
0
0
0
CH3), 3.57 (d, J1 ,1 = 11.0 Hz, 1H, H-10), 3.56 (s, 3H,
CH3), 3.56 (m, 1H, H-3), 3.541 (s, 3H, CH3), 3.535 (s, 3H,
CH3), 3.48 (s, 3H, CH3), 3.44 (s, 3H, CH3), 3.42 (d,
0
0
J1 ,1 = 11.0 Hz, 1H, H-10), 3.26 (dd, J4,3 = 9.2 Hz,
J4,5 = 9.8 Hz, 1H, H-4), 3.18 (dd, J2,1 = 3.7 Hz,
J2,3 = 9.6 Hz, 1H, H-2) ppm; 13C NMR: d = 167.25
(C=O), 166.87 (C=O), 158.47, 158.42 (2 9 C–Ar), 134.88,
134.88, 131.03, 130.99 (4 9 C-isophthalic), 130.48,
129.80 (2 9 C–Ar), 129.71 (C-isophthalic), 129.71 (2C-
Ar), 128.59 (2C-Ar), 123.88 (C-isophthalic), 114.80 (2C-
Ar), 114.71 (2C-Ar), 103.74 (C-20), 88.89 (C-1), 84.64 (C-
30), 83.72 (C-40), 83.28 (C-3), 81.68 (C-2), 79.84 (C-4),
78.89 (C-50), 74.22 (C-10), 69.77 (C-5), 69.44 (C-60), 67.69
(C-6), 60.71, 60.50, 59.38, 58.82, 58.69, 58.44
(6 9 OCH3), 43.72, 43.39 (2 9 CH2N) ppm; HRMS
(ESI): calcd for C40H50N2O13Na [M ? Na]? 789.3202,
found 789.3203.
0
0
H-50, H-6, H-60), 4.08 (d, J3 ,4 = 7.7 Hz, 1H, H-30), 4.05
0
0
(dd, J6,6 = 10.2 Hz, J6,5 = 3.9 Hz, 1H, H-6), 3.90 (dd,
0
J4 ,3 = 7.7 Hz, J4 ,5 = 7.7 Hz, 1H, H-40), 3.64 (s, 3H,
0
0
0
CH3), 3.58 (d, J1 ,1 = 11.0 Hz, 1H, H-10), 3.52
(dd, J3,2 = 9.4 Hz, J3,4 = 9.2 Hz, 1H, H-3), 3.50 (s, 3H,
CH3), 3.48 (s, 3H, CH3), 3.45 (s, 3H, CH3), 3.41 (s,
0
0
3H, CH3), 3.41 (d, J1 ,1 = 11.0 Hz, 1H, H-10), 3.34 (s, 3H,
CH3), 3.29 (dd, J4,3 = 9.2 Hz, J4,5 = 10.1 Hz, 1H, H-4),
3.19 (dd, J2,1 = 3.7 Hz, J2,3 = 9.4 Hz, 1H, H-2) ppm; 13C
0
0
123

Synthesis of dilactams
443
6,60-Di-O-[[pyridine-1,3-diyl-bis(carbonylaminomethyl)]-
4,40-diphenyl]-10,2,3,30,4,40-hexa-O-methylsucrose
(11c, C39H49N3O13)
Open Access This article is distributed under the terms of the
Creative Commons Attribution License which permits any use, dis-
tribution, and reproduction in any medium, provided the original
author(s) and the source are credited.
White solid; yield: 97 mg (74 %); m.p.: 115 °C; TLC:
Rf = 0.37
(AcOEt);
[a]2D1 = ?28.4° cm2 g-1
;
IR:
v = 3,330, 2,982, 2,932, 2,831, 1,671, 1,613, 1,585,
1,535, 1,514, 1,449, 1,363, 1,301, 1,287, 1,248, 1,151,
1,100, 1,023, 1,003, 984, 949, 879, 827, 753, 677, 646, 603,
References
1
582 cm-1; H NMR: d = 8.35 (dd, J = 7.8 Hz, 1.2 Hz,
1. Steed JW, Atwood JL (2009) Supramolecular chemistry, 2nd edn.
Wiley, Chichester
1H, pyridine), 8.32 (dd, J = 7.8 Hz, 1.2 Hz, 1H, pyridine),
8.05 (t, J = 7.8 Hz, 1H, pyridine), 7.69 (dd, J = 4.6 Hz,
5.4 Hz, 1H, NH), 7.63 (dd, J = 4.6 Hz, 4.8 Hz, 1H, NH),
7.26 (d, J = 8.7 Hz, 2H, Ar), 7.02 (d, J = 8.7 Hz, 2H, Ar),
6.93 (d, J = 8.7 Hz, 2H, Ar), 6.73 (d, J = 8.7 Hz, 2H, Ar),
5.52 (d, J1,2 = 3.7 Hz, 1H, H-1), 4.67 (dd, J = 5.5 Hz,
14.2 Hz, 1H, CH2N), 4.57 (dd, J = 5.9 Hz, 14.9 Hz, 1H,
´
}
2. Bako P, Keglevich G, Rapi Z, Toke L (2012) Curr Org Chem
16:297
´
´ ´
3. Bako P, Mako A, Keglevich G, Kubinyi M, Pal K (2005) Tet-
rahedron Asymmetry 16:1861
´
´
}
´
´
}
4. Mako A, Szollosy A, Keglevich G, Menyhard DK, Bako P, Toke
¨
L (2008) Monatsh Chem 139:525
´
´
}
´
5. Rapi Z, Szabo T, Keglevich G, Szollosy A, Drahos L, Bako P
¨
(2011) Tetrahedron Asymmetry 22:1189
´
´
´
6. Bako T, Bako P, Keglevich G, Bathori N, Czugler M, Tatai J,
Novak T, Parlagh G, Toke L (2003) Tetrahedron Asymmetry
´
0
0
0
0
CH2N), 4.53 (dd, J6 ,5 = 6.8 Hz, J6 ,6 = 10.0 Hz, 1H,
H-60), 4.46 (dd, J = 4.2 Hz, 14.9 Hz, 1H, CH2N), 4.42
(dd, J = 4.1 Hz, 14.2 Hz, 1H, CH2N), 4.34 (ddd,
J5,6 = 1.3 Hz, J5,6 = 6.6 Hz, J5,4 = 10.3 Hz, 1H, H-5),
}
14:1917
´
´ ´ ´
}
7. Bako P, Rapi Z, Keglevich G, Szabo T, Soti PL, Vıgh T, Grun A,
Holczbauer T (2011) Tetrahedron Lett 52:1473
´
´
}
´
8. Rapi Z, Bako P, Keglevich G, Szollosy A, Drahos L, Botyanszki
A, Holczbauer T (2012) Tetrahedron Asymmetry 23:489
¨
0
0
0
0
0
0
4.24 (ddd, J5 ,6 = 3.2 Hz, J5 ,6 = 6.8 Hz, J5 ,4 = 7.6 Hz,
1H, H-50), 4.22 (dd, J6,5 = 1.3 Hz, J6,6 = 9.6 Hz, 1H,
H-6), 4.15 (dd, J4 ,3 = 7.9 Hz, J4 ,5 = 7.6 Hz, 1H, H-40),
4.12 (d, J3 ,4 = 7.9 Hz, 1H, H-30), 4.10 (dd, J6,5 = 6.6 Hz,
´ ´
9. Xie J, Menand M, Maisonneuve S, Metivier R (2007) J Org Chem
0
0
0
0
72:5980
10. Hsieh YC, Chir JL, Wu HH, Guo CQ, Wu AT (2010) Tetrahe-
dron Lett 51:109
11. Yang ST, Liao DJ, Chen SJ, Hu CH, Wu AT (2012) Analyst
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12. Jarosz S, Listkowski A (2003) J Carbohydr Chem 22:753
13. Jarosz S, Listkowski A (2006) Can J Chem 84:492
14. Lewandowski B, Jarosz S (2010) Org Lett 12:2532
15. Lewandowski B, Jarosz S (2008) Chem Commun 47:6399
16. Sansone F, Baldini L, Casnati A, Lazzarotto M, Ugozzoli F,
Ungaro R (2002) Proc Natl Acad Sci USA 99:4842
17. Kima SK, Sessler JL (2010) Chem Soc Rev 39:3784
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18. Santos SM, Costa PJ, Lankshear MD, Beer PD, Felix V (2010) J
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22. Lang T, Graf E, Kyritsakas N, Hosseini MW (2012) Chem Eur J
18:10419
0
0
0
J6,6 = 9.6 Hz, 1H, H-6), 4.08 (dd, J6 ,6 = 10.0 Hz,
0
J5 ,6 = 3.2 Hz, 1H, H-60), 3.65 (s, 3H, CH3), 3.58 (s, 6H,
0
0
CH3), 3.57 (d, J1 ,1 = 11.0 Hz, 1H, H-10), 3.55 (m, 4H,
0
0
H-3, CH3), 3.47 (s, 3H, CH3), 3.45 (s, 3H, CH3), 3.40 (d,
J1 ,1 = 11.0 Hz, 1H, H-10), 3.15 (dd, J2,1 = 3.7 Hz,
J2,3 = 9.6 Hz, 1H, H-2), 3.13 (dd, J4,3 = 8.7 Hz,
J4,5 = 10.3 Hz, 1H, H-4) ppm; 13C NMR: d = 162.90
(C=O), 162.77 (C=O), 158.49, 158.42 (2 9 C–Ar), 148.59,
148.43, 139.23 (3 9 C-pyridine), 129.70 (2C-Ar), 129.61,
129.11 (2 9 C–Ar), 128.17 (2C-Ar), 124.81, 124.76
(2 9 C-pyridine), 114.92 (2C-Ar), 114.70 (2C-Ar),
103.71 (C-20), 88.70 (C-1), 84.51 (C-40), 83.70 (C-30),
83.34 (C-3), 81.73 (C-2), 80.20 (C-4), 79.01 (C-50), 73.99
(C-10), 69.93 (C-5), 69.42 (C-60), 68.06 (C-6), 60.68, 60.47,
59.34, 58.91, 58.75, 58.42 (6 9 OCH3), 43.66, 43.06
(2 9 CH2N) ppm; HRMS (ESI): calcd for C39H49N3O13Na
[M ? Na]? 790.3158, found 790.3196.
0
0
23. Potopnyk MA, Cmoch P, Jarosz S (2012) Org Lett 14:4258
Acknowledgments The support from grant POIG.01.01.02-14-102/
09 (part-financed by the European Union within the European
Regional Development Fund) is acknowledged.
123