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. 2013 Jan 17;144(3):437–443. doi: 10.1007/s00706-012-0894-2

An efficient synthesis of novel sucrose-containing dilactams

Mykhaylo A Potopnyk 1, Sławomir Jarosz 1,✉
PMCID: PMC4495044  PMID: 26166879

Abstract

Abstract

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 dichlorides, provided the 1:1-macrocycles in good yields.

Graphical Abstract

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Keywords: Carbohydrates, Macrocycles, Alkylation, Reductions, Cyclization

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 particularly useful in planning and executing the synthesis of such chiral hosts. The different configurations and conformations of carbohydrates can be incorporated in the target macrocycle, which makes these compounds convenient chiral synthetic analogs of poly(ethylene glycol) (PEG) reagents [2].

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 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].

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.

Very recently, we reported an effective procedure for synthesis of 1′,2,3,3′,4,4′-hexa-O-methyl-6,6′-di-O-(methylsulfonyl)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 6,6′-di-O-(aminophenyl)-1′,2,3,3′,4,4′-hexa-O-methylsucroses (2a–2c). Reaction of dianilines 2a and 2b (o or m) with isophthaloyl or 2,6-pyridinedicarbonyl 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 monomers 3c, 4c [23].

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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].

Results and Discussion

In this paper we report the synthesis of new sucrose macrocyclic derivatives which are twice homologated compared with compounds 3a–3c and 4a–4c. Arylmethaneamines 9a–9c (the homologated analogs of anilines 2a–2c) were used as starting materials for the preparation of conformationally less demanding structures.

1′,2,3,3′,4,4′-Hexa-O-methyl-6,6′-di-O-(methylsulfonyl)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 carbonate to give the corresponding 6,6′-di-O-(cyanophenyl)-1′,2,3,3′,4,4′-hexa-O-methylsucroses (8a–8c) in 81–84 % yield. These compounds were quantitatively converted into the 6,6′-di-O-[(aminomethyl)phenyl]-1′,2,3,3′,4,4′-hexa-O-methylsucroses (9a–9c) by reduction with LiAlH4. The crude bis-amines 9a–9c were subjected to cyclocondensation 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 solution. In all cases a 1:1-product (10a–10c and 11a–11c) was formed in good yield (63–74 %; Fig. 1).

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Fig. 1.

Fig. 1

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Macrocyclic diamides 10a–10c and 11a–11c

In summary, we have developed a simple, rapid, and efficient procedure for preparation of sucrose-based promising optically active receptors. Because of the conformational 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

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 spectrometer. 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.

General procedure for preparation of 6,6′-di-O-(cyanophenyl)-1′,2,3,3′,4,4′-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 phase was extracted with ethyl acetate (4 × 50 cm3). Combined organic solutions were washed with water (2 × 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.

6,6′-Di-O-(2-cyanophenyl)-1′,2,3,3′,4,4′-hexa-O-methylsucrose (8a, C32H40N2O11)

Colorless oil; yield: 255 mg (81 %); TLC: R f = 0.47 (hexane/AcOEt 1:2); [α]24D = +55.9° cm2 g−1; IR: Inline graphic = 2,983, 2,934, 2,832, 2,228, 1,741, 1,599, 1,581, 1,494, 1,449, 1,374, 1,292, 1,261, 1,185, 1,164, 1,102, 1,045, 1,018, 983, 879, 835, 757, 667, 566, 497 cm−1; 1H NMR: δ = 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, J 1,2 = 3.7 Hz, 1H, H-1), 4.32–4.38 (m, 2H, 2H-6′), 4.23–4.27 (m, 3H, H-5′, 2H-6), 4.18 (m, 1H, H-5), 4.09 (d, J 3′,4′ = 6.7 Hz, 1H, H-3′), 3.90 (dd, J 4′,3′ = 6.7 Hz, J 4′,5′ = 6.1 Hz, 1H, H-4′), 3.66 (d, J 1′,1′ = 11.1 Hz, 1H, H-1′), 3.60 (s, 3H, CH3), 3.54 (s, 3H, CH3), 3.51 (dd, J 3,2 = 9.7 Hz, J 3,4 = 9.1 Hz, 1H, H-3), 3.49 (s, 3H, CH3), 3.47 (s, 3H, CH3), 3.46 (s, 3H, CH3), 3.43 (d, J 1′,1′ = 11.1 Hz, 1H, H-1′), 3.42 (s, 3H, CH3), 3.34 (dd, J 4,3 = 9.1 Hz, J 4,5 = 10.0 Hz, 1H, H-4), 3.16 (dd, J 2,1 = 3.7 Hz, J 2,3 = 9.7 Hz, 1H, H-2) ppm; 13C NMR: δ = 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 × C–Ar), 104.98 (C-2′), 102.33 (CN), 102.25 (CN), 90.02 (C-1), 85.88 (C-3′), 84.92 (C-4′), 83.12 (C-3), 81.46 (C-2), 79.16 (C-4), 78.83 (C-5′), 73.30 (C-1′), 70.42 (C-6′), 69.71 (C-5), 68.52 (C-6), 60.63, 60.47, 59.51, 58.75, 58.55, 58.46 (6 × OCH3) ppm; HRMS (ESI): calcd for C32H40N2O11Na [M + Na]+ 651.2524, found 651.2525.

6,6′-Di-O-(3-cyanophenyl)-1′,2,3,3′,4,4′-hexa-O-methylsucrose (8b, C32H40N2O11)

Colorless oil; yield: 265 mg (84 %); TLC: R f = 0.51 (hexane/AcOEt 1:2); [α]22D = +56.3° cm2 g−1; IR: Inline graphic = 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; 1H NMR: δ = 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, J 1,2 = 3.7 Hz, 1H, H-1), 4.29 (m, 1H, H-6′), 4.12–4.23 (m, 5H, H-5, H-5′, 2H-6, H-6′), 4.11 (d, J 3′,4′ = 7.6 Hz, 1H, H-3′), 3.97 (dd, J 4′,3′ = 7.6 Hz, J 4′,5′ = 7.3 Hz, 1H, H-4′), 3.64 (s, 3H, CH3), 3.61 (d, J 1′,1′ = 11.0 Hz, 1H, H-1′), 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), 3.43 (d, J 1′,1′ = 11.0 Hz, 1H, H-1′), 3.22 (dd, J = 10.2 Hz, 8.9 Hz, 1H, H-4), 3.16 (dd, J 2,1 = 3.7 Hz, J 2,3 = 9.7 Hz, 1H, H-2) ppm; 13C NMR: δ = 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 × C–Ar), 113.30 (CN), 113.16 (CN), 104.39 (C-2′), 89.39 (C-1), 85.34 (C-3′), 83.79 (C-4′), 83.21 (C-3), 81.64 (C-2), 79.47 (C-4), 78.53 (C-5′), 73.70 (C-1′), 69.66 (C-5), 69.30 (C-6′), 67.80 (C-6), 60.76, 60.58, 59.42, 58.65, 58.47, 58.43 (6 × OCH3) ppm; HRMS (ESI): calcd for C32H40N2O11Na [M + Na]+ 651.2524, found 651.2522.

6,6′-Di-O-(4-cyanophenyl)-1′,2,3,3′,4,4′-hexa-O-methylsucrose (8c, C32H40N2O11)

Colorless oil; yield: 258 mg (82 %); TLC: R f = 0.54 (hexane/AcOEt 1:2); [α]24D = +75.8° cm2 g−1; IR: Inline graphic = 2,983, 2,933, 2,831, 2,225, 1,606, 1,575, 1,509, 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: δ = 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, J 1,2 = 3.7 Hz, 1H, H-1), 4.32 (m, 1H, H-6′), 4.14–4.22 (m, 5H, H-5, 2H-6, H-5′, H-6′), 4.10 (d, J 3′,4′ = 7.5 Hz, 1H, H-3′), 3.93 (dd, J 4′,3′ = 7.5 Hz, J 4′,5′ = 7.3 Hz, 1H, H-4′), 3.62 (s, 3H, CH3), 3.61 (d, J 1′,1′ = 10.8 Hz, 1H, H-1′), 3.52 (s, 3H, CH3), 3.49 (s, 3H, CH3), 3.49 (dd, J 3,2 = 9.7 Hz, J 3,4 = 8.9 Hz, 1H, H-3), 3.435 (s, 3H, CH3), 3.432 (s, 3H, CH3), 3.427 (d, J 1′,1′ = 10.8 Hz, 1H, H-1′), 3.418 (s, 3H, CH3), 3.20 (dd, J 4,3 = 8.9 Hz, J 4,5 = 9.7 Hz, 1H, H-4), 3.15 (dd, J 2,1 = 3.7 Hz, J 2,3 = 9.7 Hz, 1H, H-2) ppm; 13C NMR: δ = 161.92, 161.89, 134.11, 133.93, 119.03, 118.94, 115.33, 115.27 (12 × C–Ar), 104.54 (CN), 104.50 (C-2′), 104.36 (CN), 89.46 (C-1), 85.35 (C-3′), 83.64 (C-4′), 83.24 (C-3), 81.70 (C-2), 79.47 (C-4), 78.49 (C-5′), 73.68 (C-1′), 69.51 (C-5), 69.33 (C-6′), 67.78 (C-6), 60.78, 60.63, 59.46, 58.72, 58.51, 58.39 (6 × OCH3) ppm; HRMS (ESI): calcd for C32H40N2O11Na [M + Na]+ 651.2524, found 651.2538.

General procedure for synthesis of 6,6′-di-O-[4-(aminomethyl)phenyl]-1′,2,3,3′,4,4′-hexa-O-methylsucroses (9a–9c)

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 temperature. 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 × 40 cm3). The combined organic solutions were dried, concentrated, and the crude product was used in the next step without purification.

General procedure for syntheses of macrocyclic diamides10a–10cand11a–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 1 h at room temperature. The resulting solution was concentrated 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 × 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).

6,6′-Di-O-[[benzene-1,3-diyl-bis(carbonylaminomethyl)]-2,2′-diphenyl]-1′,2,3,3′,4,4′-hexa-O-methylsucrose (10a, C40H50N2O13)

White solid; yield: 84 mg (64 %); m.p.: 134 °C; TLC: R f = 0.35 (AcOEt); [α]22D = +78.8° cm2 g−1; IR: Inline graphic = 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, 825, 753, 710, 593, 527 cm−1; 1H NMR: δ = 8.01–8.05 (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, J 1,2 = 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, 6.5 Hz, 1H, CH2N), 4.27 (dd, J 6′,6′ = 9.9 Hz, J 6′,5′ = 2.3 Hz, 1H, H-6′), 4.14–4.20 (m, 2H, H-5′, H-6), 4.08 (d, J 3′,4′ = 7.4 Hz, 1H, H-3′), 3.93–3.97 (m, 2H, H-5, H-6′), 3.76 (dd, J 6,6 = 10.0 Hz, J 6,5 = 1.5 Hz, 1H, H-6), 3.70 (dd, J 4′,5′ = 7.5 Hz, J 4′,3′ = 7.4 Hz, 1H, H-4′), 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-1′, H-4), 3.39 (s, 3H, CH3), 3.23 (s, 3H, CH3), 3.14 (d, J 1′,1′ = 11.2 Hz, 1H, H-1′), 2.75 (dd, J 2,1 = 3.3 Hz, J 2,3 = 9.5 Hz, 1H, H-2) ppm; 13C NMR: δ = 166.96 (C=O), 166.75 (C=O), 156.85, 156.81 (2 × C–Ar), 135.53, 135.42, 131.21, 130.87 (4 × C-isophthalic), 131.09, 130.84, 129.43, 129.31 (4 × C–Ar), 129.16 (C-isophthalic), 127.05, 125.73 (2 × C–Ar), 123.80 (C-isophthalic), 121.72, 121.10, 112.51, 110.99 (4 × C–Ar), 104.37 (C-2′), 90.41 (C-1), 84.70 (C-3′), 84.09 (C-4′), 82.72 (C-3), 81.31 (C-2), 78.59 (C-4), 77.87 (C-5′), 73.53 (C-1′), 70.95 (C-6′), 70.25 (C-5), 66.07 (C-6), 60.67, 60.33, 59.67, 58.87, 58.04, 57.99 (6 × OCH3), 41.53, 40.94 (2 × CH2N) ppm; HRMS (ESI): calcd for C40H50N2O13Na [M + Na]+ 789.3205, found 789.3228.

6,6′-Di-O-[[pyridine-1,3-diyl-bis(carbonylaminomethyl)]-2,2′-diphenyl]-1′,2,3,3′,4,4′-hexa-O-methylsucrose (11a, C39H49N3O13)

White solid; yield: 88 mg (67 %); m.p.: 96 °C; TLC: R f = 0.37 (AcOEt); [α]22D = +163.1° cm2 g−1; IR: Inline graphic = 3,537, 3,403, 3,303, 3,064, 2,984, 2,933, 2,831, 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, 564 cm−1; 1H NMR: δ = 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, J 1,2 = 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, J 6′,6′ = 10.2 Hz, J 6′,5′ = 3.1 Hz, 1H, H-6′), 4.22 (m, 1H, H-5′), 4.11 (d, J 3′,4′ = 6.9 Hz, 1H, H-3′), 4.01–4.07 (m, 2H, H-5, H-6), 3.98 (dd, J 6′,5′ = 7.7 Hz, J 6′,6′ = 10.2 Hz, 1H, H-6′), 3.86 (dd, J 4′,3′ = 6.9 Hz, J 4′,5′ = 6.9 Hz, 1H, H-4′), 3.76 (d, J 6,6 = 9.2 Hz, 1H, H-6), 3.57 (d, J 1′,1′ = 11.0 Hz, 1H, H-1′), 3.52 (s, 3H, CH3), 3.48 (dd, J 3,2 = 9.6 Hz, J 3,4 = 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, CH3), 3.41 (d, J 1′,1′ = 11.0 Hz, 1H, H-1′), 3.32 (dd, J 4,3 = 9.0 Hz, J 4,5 = 9.6 Hz, 1H, H-4), 3.25 (s, 3H, CH3), 2.81 (dd, J 2,1 = 3.4 Hz, J 2,3 = 9.6 Hz, 1H, H-2) ppm; 13C NMR: δ = 163.38 (C=O), 163.12 (C=O), 156.67, 156.64 (2 × C–Ar), 148.98, 148.89, 138.83 (3 × C-pyridine), 130.72, 130.02, 129.03, 128.71, 128.34, 126.42 (6 × C–Ar), 124.74, 124.74 (2 × C-pyridine), 122.67, 121.43, 114.94, 112.44 (4 × C–Ar), 104.92 (C-2′), 89.89 (C-1), 84.85 (C-3′), 84.19 (C-4′), 82.81 (C-3), 81.88 (C-2), 79.03 (C-4), 78.69 (C-5′), 73.65 (C-1′), 72.06 (C-6′), 70.26 (C-5), 67.30 (C-6), 60.48, 60.42, 59.54, 58.50, 58.38, 58.03 (6 × OCH3), 39.65, 38.14 (2 × CH2N) ppm; HRMS (ESI): calcd for C39H49N3O13Na [M + Na]+ 790.3158, found 790.3165.

6,6′-Di-O-[[benzene-1,3-diyl-bis(carbonylaminomethyl)]-3,3′-diphenyl]-1′,2,3,3′,4,4′-hexa-O-methylsucrose (10b, C40H50N2O13)

White solid; yield: 82 mg (63 %); m.p.: 111 °C; TLC: R f = 0.36 (AcOEt); [α]22D = +59.8° cm2 g−1; IR: Inline graphic = 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, 622 cm−1; 1H NMR: δ = 7.97–8.01 (m, 2H, isophthalic), 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, J 1,2 = 3.8 Hz, 1H, 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 × H-6′), 4.06–4.12 (m, 1H, H-5′), 4.09 (d, J 3′,4′ = 8.0 Hz, 1H, H-3′), 4.03 (br d, J 6,6 = 9.1 Hz, 1H, H-6), 3.97 (dd, J 4′,3′ = 8.0 Hz, J 4′,5′ = 8.0 Hz, 1H, H-4′), 3.61 (s, 3H, CH3), 3.58 (d, J 1′,1′ = 10.9 Hz, 1H, H-1′), 3.49 (s, 3H, CH3), 3.48 (dd, J 3,2 = 9.6 Hz, J 3,4 = 9.3 Hz, 1H, H-3), 3.45 (s, 3H, CH3), 3.42 (d, J 1′,1′ = 10.9 Hz, 1H, H-1′), 3.41 (s, 6H, 2CH3), 3.40 (s, 3H, CH3), 3.36 (dd, J 4,3 = 9.3 Hz, J 4,5 = 9.6 Hz, 1H, H-4), 3.21 (dd, J 2,1 = 3.8 Hz, J 2,3 = 9.6 Hz, 1H, H-2) ppm; 13C NMR: δ = 166.71 (C=O), 166.34 (C=O), 159.20, 159.01, 139.63, 139.28 (4 × C–Ar), 134.69, 134.56 (2 × C-isophthalic), 130.78 (2C-isophthalic), 129.79, 129.77 (2 × C–Ar), 129.39, 124.05 (2 × C-isophthalic), 121.64, 120.80, 115.13, 114.48, 113.75, 112.49 (6 × C–Ar), 104.15 (C-2′), 88.69 (C-1), 85.02 (C-3′), 83.17 (C-3), 83.03 (C-4′), 81.29 (C-2), 79.14 (C-4), 78.08 (C-5′), 74.83 (C-1′), 69.66 (C-5), 68.95 (C-6′), 66.30 (C-6), 60.65, 60.46, 59.41, 58.59, 58.39, 58.03 (6 × OCH3), 44.25, 43.95 (2 × CH2N) ppm; HRMS (ESI): calcd for C40H50N2O13Na [M + Na]+ 789.3202, found 789.3214.

6,6′-Di-O-[[pyridine-1,3-diyl-bis(carbonylaminomethyl)]-3,3′-diphenyl]-1′,2,3,3′,4,4′-hexa-O-methylsucrose (11b, C39H49N3O13)

White solid; yield: 86 mg (66 %); m.p.: 125 °C; TLC: R f = 0.39 (AcOEt); [α]22D = +61.6° cm2 g−1; IR: Inline graphic = 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, 876, 844, 755, 682, 647, 623 cm−1; 1H NMR: δ = 8.34–8.38 (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, J 1,2 = 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-6′), 4.21 (ddd, J 5,4 = 10.1 Hz, J 5,6 = 3.9 Hz, J 5,6 = 1.6 Hz, 1H, H-5), 4.10–4.17 (m, 3H, H-5′, H-6, H-6′), 4.08 (d, J 3′,4′ = 7.7 Hz, 1H, H-3′), 4.05 (dd, J 6,6 = 10.2 Hz, J 6,5 = 3.9 Hz, 1H, H-6), 3.90 (dd, J 4′,3′ = 7.7 Hz, J 4′,5′ = 7.7 Hz, 1H, H-4′), 3.64 (s, 3H, CH3), 3.58 (d, J 1′,1′ = 11.0 Hz, 1H, H-1′), 3.52 (dd, J 3,2 = 9.4 Hz, J 3,4 = 9.2 Hz, 1H, H-3), 3.50 (s, 3H, CH3), 3.48 (s, 3H, CH3), 3.45 (s, 3H, CH3), 3.41 (s, 3H, CH3), 3.41 (d, J 1′,1′ = 11.0 Hz, 1H, H-1′), 3.34 (s, 3H, CH3), 3.29 (dd, J 4,3 = 9.2 Hz, J 4,5 = 10.1 Hz, 1H, H-4), 3.19 (dd, J 2,1 = 3.7 Hz, J 2,3 = 9.4 Hz, 1H, H-2) ppm; 13C NMR: δ = 163.14 (C=O), 163.08 (C=O), 159.16, 158.93 (2 × C–Ar), 148.63, 148.54 (2 × C-pyridine), 139.25, 139.13 (2 × C–Ar), 139.13 (C-pyridine), 129.96, 129.92 (2 × C–Ar), 125.17, 125.14 (2 × C-pyridine), 121.11, 120.84, 114.41, 114.17, 113.74, 112.95 (6 × C–Ar), 104.07 (C-2′), 89.93 (C-1), 84.93 (C-3′), 83.61 (C-4′), 83.23 (C-3), 81.51 (C-2), 79.45 (C-4), 78.37 (C-5′), 74.19 (C-1′), 69.70 (C-5), 69.23 (C-6′), 66.77 (C-6), 60.69, 60.47, 59.34, 58.53, 58.41, 58.22 (6 × OCH3), 43.66, 43.63 (2 × CH2N) ppm; HRMS (ESI): calcd for C39H49N3O13Na [M + Na]+ 790.3158, found 790.3125.

6,6′-Di-O-[[benzene-1,3-diyl-bis(carbonylaminomethyl)]-4,4′-diphenyl]-1′,2,3,3′,4,4′-hexa-O-methylsucrose (10c, C40H50N2O13)

White solid; yield: 93 mg (71 %); m.p.: 144 °C; TLC: R f = 0.35 (AcOEt); [α]24D = +58.2° cm2 g−1; IR: Inline graphic = 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: δ = 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, J 1,2 = 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-6′, CH2N), 4.32 (dd, J = 13.8 Hz, 4.8 Hz, 1H, CH2N), 4.28 (m, 1H, H-5), 4.20 (ddd, J 5′,4′ = 8.3 Hz, J 5′,6′ = 6.7 Hz, J 5′,6′ = 3.3 Hz, 1H, H-5′), 4.14 (d, J 3′,4′ = 7.9 Hz, 1H, H-3′), 4.13 (m, 1H, H-6), 4.09 (dd, J 6,6 = 9.8 Hz, J 6,5 = 5.3 Hz, 1H, H-6), 4.05 (dd, J 6′,6′ = 9.9 Hz, J 6′,5′ = 3.3 Hz, 1H, H-6′), 4.03 (dd, J 4′,3′ = 7.9 Hz, J 4′,5′ = 8.3 Hz, 1H, H-4′), 3.65 (s, 3H, CH3), 3.57 (d, J 1′,1′ = 11.0 Hz, 1H, H-1′), 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, J 1′,1′ = 11.0 Hz, 1H, H-1′), 3.26 (dd, J 4,3 = 9.2 Hz, J 4,5 = 9.8 Hz, 1H, H-4), 3.18 (dd, J 2,1 = 3.7 Hz, J 2,3 = 9.6 Hz, 1H, H-2) ppm; 13C NMR: δ = 167.25 (C=O), 166.87 (C=O), 158.47, 158.42 (2 × C–Ar), 134.88, 134.88, 131.03, 130.99 (4 × C-isophthalic), 130.48, 129.80 (2 × 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-2′), 88.89 (C-1), 84.64 (C-3′), 83.72 (C-4′), 83.28 (C-3), 81.68 (C-2), 79.84 (C-4), 78.89 (C-5′), 74.22 (C-1′), 69.77 (C-5), 69.44 (C-6′), 67.69 (C-6), 60.71, 60.50, 59.38, 58.82, 58.69, 58.44 (6 × OCH3), 43.72, 43.39 (2 × CH2N) ppm; HRMS (ESI): calcd for C40H50N2O13Na [M + Na]+ 789.3202, found 789.3203.

6,6′-Di-O-[[pyridine-1,3-diyl-bis(carbonylaminomethyl)]-4,4′-diphenyl]-1′,2,3,3′,4,4′-hexa-O-methylsucrose (11c, C39H49N3O13)

White solid; yield: 97 mg (74 %); m.p.: 115 °C; TLC: R f = 0.37 (AcOEt); [α]21D = +28.4° cm2 g−1; IR: Inline graphic = 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, 582 cm−1; 1H NMR: δ = 8.35 (dd, J = 7.8 Hz, 1.2 Hz, 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, J 1,2 = 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, CH2N), 4.53 (dd, J 6′,5′ = 6.8 Hz, J 6′,6′ = 10.0 Hz, 1H, H-6′), 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, J 5,6 = 1.3 Hz, J 5,6 = 6.6 Hz, J 5,4 = 10.3 Hz, 1H, H-5), 4.24 (ddd, J 5′,6′ = 3.2 Hz, J 5′,6′ = 6.8 Hz, J 5′,4′ = 7.6 Hz, 1H, H-5′), 4.22 (dd, J 6,5 = 1.3 Hz, J 6,6 = 9.6 Hz, 1H, H-6), 4.15 (dd, J 4′,3′ = 7.9 Hz, J 4′,5′ = 7.6 Hz, 1H, H-4′), 4.12 (d, J 3′,4′ = 7.9 Hz, 1H, H-3′), 4.10 (dd, J 6,5 = 6.6 Hz, J 6,6 = 9.6 Hz, 1H, H-6), 4.08 (dd, J 6′,6′ = 10.0 Hz, J 5′,6′ = 3.2 Hz, 1H, H-6′), 3.65 (s, 3H, CH3), 3.58 (s, 6H, CH3), 3.57 (d, J 1′,1′ = 11.0 Hz, 1H, H-1′), 3.55 (m, 4H, H-3, CH3), 3.47 (s, 3H, CH3), 3.45 (s, 3H, CH3), 3.40 (d, J 1′,1′ = 11.0 Hz, 1H, H-1′), 3.15 (dd, J 2,1 = 3.7 Hz, J 2,3 = 9.6 Hz, 1H, H-2), 3.13 (dd, J 4,3 = 8.7 Hz, J 4,5 = 10.3 Hz, 1H, H-4) ppm; 13C NMR: δ = 162.90 (C=O), 162.77 (C=O), 158.49, 158.42 (2 × C–Ar), 148.59, 148.43, 139.23 (3 × C-pyridine), 129.70 (2C-Ar), 129.61, 129.11 (2 × C–Ar), 128.17 (2C-Ar), 124.81, 124.76 (2 × C-pyridine), 114.92 (2C-Ar), 114.70 (2C-Ar), 103.71 (C-2′), 88.70 (C-1), 84.51 (C-4′), 83.70 (C-3′), 83.34 (C-3), 81.73 (C-2), 80.20 (C-4), 79.01 (C-5′), 73.99 (C-1′), 69.93 (C-5), 69.42 (C-6′), 68.06 (C-6), 60.68, 60.47, 59.34, 58.91, 58.75, 58.42 (6 × OCH3), 43.66, 43.06 (2 × CH2N) ppm; HRMS (ESI): calcd for C39H49N3O13Na [M + Na]+ 790.3158, found 790.3196.

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.

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