Designer dendrimers: Branched oligosulfonimides with controllable molecular architectures

Article abstract of DOI:10.1021/ja061606b

The synthesis of "designer" dendrimers and dendrons with sulfonimide units at every branching point is reported. The synthesis is based on a series of (regio)selective functionalization reactions of amines and sulfonamides allowing precise control of the

Full text of DOI:10.1021/ja061606b

SUPPORTING INFORMATION
Designer Dendrimers: Branched Oligosulfonimides with Controllable
Molecular Architectures
Oleg Lukin,*[a] Volker Gramlich,[a] Ramchandra Kandre,[a] Igor Zhun,[a] Thorsten
Felder,[b,c] Christoph A. Schalley[c] and Grigory Dolgonos [d]
[a] Institute of Polymers, Department of Materials, ETH Zurich, 8093 Zurich, Switzerland;
E-mail: oleg.lukin@mat.ethz.ch; Fax: +41 44 633 13 97
[b]
Kekulé-Institut für Organische Chemie und Biochemie der Universität, Gerhard-
Domagk-Strasse 1, 53121 Bonn, Germany
[c] Institut für Chemie und Biochemie - Organische Chemie, Freie Universität, Takustr. 3,
14195 Berlin, Germany
[d]
Centre for Research in Molecular Modeling, Department of Chemistry and
Biochemistry, Concordia University, Montréal, Québec, Canada, H3G 1M8
Experimental Section
Instruments and methods: Melting points were determined on a Büchi microscope
heating unit and are uncorrected. NMR spectra were measured on Bruker AMX 300 or
DRX 500 spectrometers. All chemical shifts are given in ppm with the solvent signals
taken as internal standards; coupling constants are in hertz. EI mass spectra were obtained
with Micromass Autospec Q spectrometer and MALDI mass spectra were recorded on a
Micromass MALDI-Tof Spec E mass spectrometer equipped with an N2 laser (337 nm).
ESI mass spectra and MS/MS spectra were recorded on a Bruker APEX IV Fourier-
transform ion-cyclotron-resonance (FT-ICR) mass spectrometer with an Apollo
electrospray ion source equipped with an off-axis 70° spray needle.
Comment on dendrimer solubilities.
Oligosulfonimide dendrimers and dendrons of all generations bearing peripheral tosyl-
and 2-naphthylsulfonyl groups exhibit very high solubilities in both polar aprotic and
apolar aprotic (except for hexane) solvents. Their solubilities in DMF, THF, chloroform
and benzene are in the range of 150-250 mg/mL. Nosyl-decorated branched sulfonimides
show poor solubility in the above mentioned solvents at r.t. with the exception of 1st
generation species as well as Janus-type dendrimers. The compounds with peripheral
nitro-groups can be dissolved in hot THF and hot chloroform. All the above mentioned
compounds have low or no solubility in methanol and ethanol. Oligosulfonimides bearing
peripheral amino-groups are soluble in alcohols or mixtures of alcohols with either
chlorinated solvents or benzene.
General synthetic procedures:
S1

Persulfonylation of amines and sulfonamides with arylsulfonyl chlorides
(preparation of compounds 2a, 3a, 4, 6a, 7, 9c, 10a, 11, 12a, 13a, b, 15a, b, 17a, b): A
mixture of a corresponding amine or sulfonamide, triethylamine (ca. fourfold molar
excess per amino or sulfonamide group) and arylsulfonyl chloride (ca. threefold molar
excess per amino or sulfonamide group) was stirred in dichloromethane at reflux for 2 to
24 hrs, dependently on the number of amino groups in a compound. Then the solvent was
removed under reduced pressure and the residue was triturated with methanol. The solid
precipitate was filtered through a glass filter and thoroughly washed with methanol. The
resulting solid powders were dried in vacuum and then, if necessary, purified by
chromatography on silica gel.
Persulfonylation of aromatic amines with arylsulfonyl chlorides (preparation of
compounds 8a, 9a): The procedure is fully analogous to the previous one with the
exception of strict stoichiometric amount of the arylsulfonyl chloride added (two
equivalents per amino group).
Reduction of nitro-derivatives with tin (II) chloride dihydrate (preparation of
.
compounds 5b, 12b, 14): A mixture of a nitro-compound and SnCl2 2H2O (four
equivalents per nitro group) was boiled in a mixture of ethanol and concentrated
hydrochloric acid (5 mL per gram of nitro-compound) for 5 hrs, cooled, and then poured
onto ice. The pH was adjusted to 10 with 2 M aqueous NaOH, and the released amine
was extracted with dichloromethane, dried over MgSO4, and then evaporated to give
corresponding amines as colorless solids.
Catalytic reduction of nitro-derivatives with H2 (preparation of compounds 2b, 3b,
6b, 8b, 9d, 10b): A nitro-compound was dissolved in a 2:1 mixture of benzene/ethanol.
To this solution was added a catalytic amount of commercial 10% Pd/C that had been
previously washed with ethanol. The resulting suspension was evacuated and the reaction
flask was filled with H2. This operation was repeated three times and the mixture was
stirred for 24 hrs at room temperature under hydrogen pressure of 3 bar. Then the
palladium catalyst was filtered off in a vacuum through a pad of Celite and rinsed with a
2:1 mixture of benzene/ethanol. The filtrates were combined and evaporated in vacuum to
give a colorless solid. The yields of the catalytic hydrogenation are assumed quantitative.
General procedure for the Suzuki-Miyaura cross-coupling (preparation of
compounds 18-20): Aryl bromide (0.34 mmol, compounds 13b, 15b and 17b) and
benzene-1,4-bis(boronic acid)propane-1,3-diol diester (0.17 mmol) were dissolved in 10
mL of dry THF. A concentrated solution of NaHCO3 in water (5 mL) was added to the
reaction mixture and the system was degassed. Freshly prepared Pd[P(p-tolyl)3]3 (10-14
mg) was added and the reaction mixture was allowed to stir at 80°C for 24 hrs under
nitrogen atmosphere. Then 20 mL of water were added and the emulsion was taken up
with 100 mL of dichloromethane. The organic layer was separated, washed with water
and brine, dried over Mg2SO4 and evaporated. The brown viscous residue was
chromatographed on silica gel column with hexane/ethylacetate (2:1) eluant.
S2

N-n-octyl-4-nitrobenzenesulfonimide 2a: 1.0 g of octylamine 1 was used in the
1
reaction. Recrystallized from methanol; yield 3.68 g (95%); m.p. 131-132 °C; H NMR
(300 MHz, CDCl3): = 0.91 (t, 3JH, H = 6.9 Hz, 3 H, CH3), 1.27 (s, 10 H, CH2), 1.71 (br.
2H, CH2), 3.78 (m, 2 H, CH2), 8.30 (d, 3JH, H = 9.0 Hz, 4 H, ArH), 8.46 (d, 3JH, H = 9.0 Hz,
13
4 H, ArH) ppm; C NMR (75.47 MHz, CDCl3): = 14.05, 22.58, 26.45, 28.87, 29.07,
29.95, 31.66, 50.37, 124.45, 129.69, 145.05, 150.82 ppm; MS (EI, 80 eV): m/z = 499.11
[M]+, 399.99 [M – C7H15]+, 313.12 [M – p-NO2C6H4SO2]+, 185.99 [M – p-
NO2C6H4SO2NC8H17]+; elemental analysis calcd (%) for C20H25N3O8S2 (499.56): C
48.09, H 5.04, N 8.41, S 12.84; found C 48.26, H 5.08, N 8.27, S 13.02.
1
N-n-octyl-4-aminobenzenesulfonimide 2b: M.p. 149-150 °C; H NMR (300 MHz,
CD3OD): = 0.93 (t, 3JH, H = 7.0 Hz, 3 H, CH3), 1.27 (s, 10 H, CH2), 1.61 (br. 2H, CH2),
3
3
3.54 (m, 2 H, CH2), 6.68 (d, JH, H = 8.4 Hz, 4 H, ArH), 7.52 (d, JH, H = 8.4 Hz, 4 H,
ArH) ppm; MS (ESI pos., CH3OH): m/z = 440.20 [M+H]+ calcd monoisotopic peak
(12C20 H3014N3 O4 S2) 440.16; 462.10 [M+Na]+ (12C20 H2914N3 O4 S2Na) calcd
1
16
32
1
16
32
monoisotopic peak 462.16.
N-n-octyl-4-(4-nitrobenzenesulfonimido)benzenesulfonimide 3a: 2.7 g of diamine
2b were used in the reaction; yield 5.20 g (71%), m.p. 209-211 °C. 1H NMR (300 MHz,
3
(CD3)2SO): = 0.83 (t, JH, H = 7.0 Hz, 3 H, CH3), 1.23 (s, 10 H, CH2), 1.58 (br. 2H,
CH2), 3.81 (br, 2 H, CH2), 7.50 (d, 3JH, H = 8.7 Hz, 4 H, ArH), 8.02 (d, 3JH, H = 8.7 Hz, 4
H, ArH), 8.14 (d, 3JH, H = 9.0 Hz, 8 H, ArH), 8.51 (d, 3JH, H = 9.0 Hz, 8 H, ArH) ppm; 13C
NMR (75.47 MHz, (CD3)2SO): = 13.90, 22.01, 25.83, 28.33, 28.54, 31.14, 49.39,
125.14, 129.52, 130.04, 132.72, 137.55, 140.97, 142.47, 151.09 ppm; elemental analysis
calcd (%) for C44H41N7O20S6 (1180.22): C 44.78, H 3.50, N 8.31, S 16.30; found C 44.56,
H 3.48, N 8.07, S 16.12.
N-n-octyl-4-(4-aminobenzenesulfonimido)benzenesulfonimide 3b: M.p. 145-147 °C;
3
1H NMR (300 MHz, (CD3)2SO): = 0.85 (t, JH, H = 7.0 Hz, 3 H, CH3), 1.23 (s, 10 H,
3
CH2), 1.53 (br. 2H, CH2), 3.75 (br, 2 H, CH2), 6.41 (br. 8 H, NH2), 6.62 (d, JH, H = 8.8
3
3
Hz, 8 H, ArH), 7.27 (d, JH, H = 8.7 Hz, 4 H, ArH), 7.34 (d, JH, H = 8.8 Hz, 8 H, ArH),
3
7.93 (d, JH, H = 8.7 Hz, 4 H, ArH) ppm. MS (ESI pos., CH3OH/CH2Cl2): m/z = 1082.16
[M+Na]+ calcd monoisotopic peak (12C44 H4914N7 O1232S6Na) 1082.17; 1098.14 [M+K]+
1
16
calcd monoisotopic peak (12C44 H4914N7 O1232S6K) 1098.14.
1
16
Compound 4: 1 g of tetraaminoderivative 3b was used for the reaction. The crude
product was purified by column chromatography and then recrystallized from
CH2Cl2/CH3OH. Rf = 0.24 (silica gel, CH2Cl2); yield 1.22 g (57%); m.p. 151-155 °C; 1H
3
NMR (500 MHz, CDCl3): = 0.88 (t, JH, H = 7.0 Hz, 3 H, CH3), 1.27 (s, 10 H, CH2),
1.69 (br. 2 H, CH2), 2.47 (s, 24 H, CH3), 3.71 (t, 3JH, H = 7.5 Hz, 2 H, CH2), 7.19 (d, 3JH, H
3
3
= 8.7 Hz, 4 H, ArH), 7.24 (d, JH, H = 8.7 Hz, 8 H, ArH), 7.37 (d, JH, H = 8.0 Hz, 16 H,
3
13
ArH), 7.81-7.84 (m, 24 H, ArH), 8.04 (d, JH, H = 8.7 Hz, 4 H, ArH) ppm; C NMR
(75.47 MHz, CDCl3): = 14.15, 21.83, 22.64, 26.59, 28.96, 29.15, 31.72, 50.29, 128.65,
129.46, 129.62, 129.99, 132.42, 132.63, 136.00, 138.61, 139.57, 140.24, 141.67, 145.83
ppm. MS (ESI pos., CH3OH/CH2Cl2): m/z = 2330.21 [M+K]+ calcd monoisotopic peak
(12C100 H9714N7 O28 S14K) 2330.21; 2314.23 [M+Na]+ calcd monoisotopic peak
1
16
32
S3

1
16
32
(12C100 H9714N7 O28 S14Na) 2314.24; elemental analysis calcd (%) for C100H97N7O28S14
(2293.78): C 52.36, H 4.26, N 4.27, S 19.57; found C 52.32, H 4.60, N 4.13, S 18.95.
N-n-octyl-4-nitrobenzenesulfonamide 5a: n-octylamine (5 g, 39 mmol) and
triethylamine (7 mL, 22 mmol) were dissolved in dry dichloromethane (200 mL). To the
stirred mixture a solution of 4-nitrobenzenesulfonyl chloride (8.6 g, 39 mmol) in 60 mL
of dry dichloromethane was added over a period of 10 min. The reaction mixture was
allowed to stir for 20 min at room temperature and then the solvent was removed under
reduced pressure. The viscous residue was triturated with 200 mL of methanol/water
(5:1) and allowed to stand for 1 hr. Precipitated white flakes were filtered through a glass
filter and thoroughly washed with 5% solution of hydrochloric acid and then with large
amount of deionized water. The colorless crystalline solid was dried in vacuum resulting
in 10.6 g (89%); m.p. 71-73 °C; 1H NMR (300 MHz, CDCl3): = 0.88 (t, 3JH, H = 7.0 Hz,
3 H, CH3), 1.24 (s, 10 H, CH2), 1.50 (br. 2 H, CH2), 3.02 (m, 2 H, CH2), 4.79 (t, 3JH, H
=
6.0 Hz, 1 H, NH), 8.08 (d, 3JH, H = 9.0 Hz, 2 H, ArH), 8.39 (d, 3JH, H = 9.0 Hz, 2 H, ArH)
ppm; 13C NMR (75.47 MHz, CDCl3): = 14.04, 22.58, 26.45, 28.97, 29.07, 29.63, 31.68,
43.42, 124.41, 128.31, 146.03, 150.04 ppm. MS (EI, 80 eV): m/z = 314.12 [M]+;
elemental analysis calcd (%) for C14H22N2O4S (314.40): C 53.48, H 7.05, N 8.91, S
10.20; found C 53.39, H 6.89, N 8.99, S 10.33.
N-n-octyl-4-aminobenzenesulfonamide 5b: 5 g of 5a were used in the reaction. Yield
4.45 g (98%); m.p. 71-73 °C. 1H NMR (300 MHz, CD3OD): = 0.84 (t, 3JH, H = 7.0 Hz, 3
3
H, CH3), 1.98 (s, 10 H, CH2), 1.41 (br. 2 H, CH2), 2.81 (m, 2 H, CH2), 6.78 (d, JH, H
=
3
13
8.7 Hz, 2 H, ArH), 7.59 (d, JH, H = 8.7 Hz, 2 H, ArH) ppm; C NMR (75.47 MHz,
CD3OD): = 13.03, 22.29, 26.29, 28.82, 28.88, 29.28, 31.55, 42.70, 121.52, 128.60,
138.22, 138.45 ppm; MS (EI, 80 eV): m/z = 284.14 [M]+.
Compound 6a: 2 g of 5b were used for the reaction. Yield 3.84 g (66%); m.p. 178-181
1
3
°C; H NMR (300 MHz, CDCl3): = 0.90 (t, JH, H = 6.9 Hz, 3 H, CH3), 1.28 (s, 10 H,
CH2), 1.73 (br. 2H, CH2), 3.79 (t, 3JH, H = 7.5 Hz, 2 H, CH2), 7.30 (d, 3JH, H = 8.7 Hz, 2 H,
ArH), 8.16 (d, 3JH, H = 9.0 Hz, 2 H, ArH), 8.18 (d, 3JH, H = 9.0 Hz, 4 H, ArH), 8.29 (d, 3JH,
= 8.7 Hz, 2 H, ArH), 8.46 (d, JH, H = 9.0 Hz, 2 H, ArH), 8.48 (d, 3JH, H = 9.0 Hz, 4 H,
3
H
13
ArH) ppm; NMR C (75.47 MHz, (CD3)2SO): = 13.87, 22.01, 25.77, 28.28, 28.51,
29.44, 31.11, 49.87, 124.85, 125.14, 129.46, 129.51, 130.04, 132.80, 137.59, 140.96,
142.54, 143.96, 150.68, 151.11 ppm; MS (EI, 80 eV): m/z = 839.09 [M]+, 653.13 [M – p-
NO2C6H4SO2]+, 525.99 [M – p-NO2C6H4SO2NC8H17]+, 469.15 [M – 2 p-NO2C6H4SO2]+;
elemental analysis calcd (%) for C32H33N5O14S4 (839.89): C 45.76, H 3.96, N 8.34, S
15.27; found C 46.03, H 4.17, N 8.47, S 15.40.
1
3
Compound 6b: M.p. 125-128 °C; H NMR (300 MHz, CD3OD): = 0.90 (t, JH, H
=
6.9 Hz, 3 H, CH3), 1.26 (br. 10 H, CH2), 1.62 (br. 2H, CH2), 3.62 (t, 3JH, H = 6.9 Hz, 2 H,
CH2), 6.66 (d, 3JH, H = 7.2 Hz, 6 H, ArH), 7.19 (d, 3JH, H = 8.1 Hz, 2 H, ArH), 7.43 (d, 3JH,
3
= 7.2 Hz, 4 H, ArH), 7.83 (d, JH, H = 8.1 Hz, 2 H, ArH) ppm; MS (EI, 80 eV): m/z =
H
749.20 [M]+, 594.16 [M – p-NH2C6H4SO2]+, 439.16 [M – 2 p-NH2C6H4SO2]+.
S4

Compound 7: 0.93 g of the triamine 6b were used for the reaction.The product was
purified by column chromatography. (Rf = 0.31, silica gel, CH2Cl2); Yield 1.41 g (70%).
1
3
M.p. 135-137 °C; H NMR (500 MHz, CDCl3): = 0.88 (t, JH, H = 7.0 Hz, 3 H, CH3),
1.27 (s, 10 H, CH2), 1.69 (br. 2 H, CH2), 2.47 (s, 18 H, CH3), 3.71 (t, 3JH, H = 7.5 Hz, 2 H,
CH2), 7.19 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.25 (d, 3JH, H = 8.7 Hz, 6 H, ArH), 7.37 (d, 3JH,
= 8.0 Hz, 4 H, ArH), 7.39 (d, JH, H = 8.0 Hz, 8 H, ArH), 7.81-7.85 (m, 16 H, ArH),
7.96 (d, JH, H = 8.7 Hz, 2 H, ArH), 8.04 (d, JH, H = 8.7 Hz, 2 H, ArH) ppm; C NMR
(75.47 MHz, CDCl3): = 14.17, 21.84, 22.67, 26.64, 29.00, 29.20, 30.12, 31.77, 50.18,
128.15, 128.67, 129.11, 129.55, 129.63, 129.94, 130.01, 132.39, 132.53, 132.65, 136.04,
136.09, 138.51, 139.58, 139.61, 140.26, 140.86, 141.86, 145.74, 145.85 ppm; MS (ESI
3
H
3
3
13
pos., CH3OH/CH2Cl2): m/z
=
1712.18 [M+K]+ calcd monoisotopic peak
1
16
32
(12C74 H7514N516O20 S10K) 1712.18; 1696.194 [M+Na]+ calcd monoisotopic peak
1
32
(12C74 H7514N5 O20 S10Na) 1696.21; elemental analysis calcd (%) for C74H75N5O20S10
(1675.06): C 53.06, H 4.51, N 4.18, S 19.14; found C 52.87, H 4.60, N 3.83, S 19.28.
Compound 8a: 2 g of 5b were used for the reaction. Recrystallized from
1
dichloromethane/methanol; yield 1.92 g (42%); m.p. 242-244 °C; H NMR (300 MHz,
3
CDCl3): = 0.90 (t, JH, H = 6.9 Hz, 3 H, CH3), 1.28 (s, 10 H, CH2), 1.57 (br. 2H, CH2),
3.09 (m, 2 H, CH2), 4.74 (t, 3JH, H = 6.0 Hz, 1 H, NH), 7.23 (d, 3JH, H = 8.4 Hz, 2 H, ArH),
3
3
3
7.95 (d, JH, H = 8.4 Hz, 2 H, ArH), 8.18 (d, JH, H = 9.0 Hz, 4 H, ArH), 8.48 (d, JH, H
=
13
9.0 Hz, 4 H, ArH) ppm; C NMR (75.47 MHz, (CD3)2SO): = 13.91, 22.04, 26.00,
28.50, 29.06, 29.89, 31.18, 42.59, 125.12, 128.04, 129.96, 132.33, 135.58, 142.72,
143.20, 151.05 ppm. MS (EI, 80 eV): m/z = 654.10 [M]+, 463.97 [M – C8H17NH]+,
284.27 [M – 2 p-NO2C6H4SO2]+; elemental analysis calcd (%) for C26H30N4O10S3
(654.73): C 47.70, H 4.62, N 8.56, S 14.69; found C 47.48, H 4.68, N 8.41, S 14.87.
Compound 8b: M.p. 142-144 °C; 1H NMR (300 MHz, (CD3)2SO): = 0.84 (t, 3JH, H
=
6.9 Hz, 3 H, CH3), 1.20 (s, 10 H, CH2), 1.33 (br. 2H, CH2), 2.77 (m, 2 H, CH2), 6.38 (s, 4
H, NH2), 6.60 (d, 3JH, H = 7.2 Hz, 4 H, ArH), 7.15 (d, 3JH, H = 8.4 Hz, 2 H, ArH), 7.32 (d,
3JH, H = 7.2 Hz, 4 H, ArH), 7.72 (s, 1 H, NH), 7.78 (d, 3JH, H = 8.4 Hz, 2 H, ArH) ppm; 13C
NMR (75.47 MHz, (CD3)2SO): = 13.95, 22.06, 26.01, 28.50, 28.56, 29.00, 31.20,
42.59, 112.40, 122.41, 127.28, 130.33, 132.17, 138.01, 141.71, 154.35 ppm; MS (EI, 80
eV): m/z = 594.16 [M]+, 439.16 [M – p-NH2C6H4SO2]+, 284.27 [M – 2 p-NO2C6H4SO2]+.
Compound 9a: 2.5 g of diamine 8b were used in the reaction. Purified by column
chromatography (Rf = 0.32, silica gel, CH2Cl2); yield 2.70 g (48%); m.p. 157-159 °C; 1H
3
NMR (500 MHz, CDCl3): = 0.83 (t, JH, H = 6.9 Hz, 3 H, CH3), 1.20 (s, 10 H, CH2),
1.45 (br. 2H, CH2), 2.95 (m, 2 H, CH2), 4.39 (t, 3JH, H = 6.0 Hz, 1 H, NH), 7.08 (d, 3JH, H
=
8.7 Hz, 2 H, ArH), 7.23 (d, 3JH, H = 8.7 Hz, 4 H, ArH), 7.63-7.70 (m, 8 H, ArH), 7.74 (d,
3JH, H = 8.7 Hz, 4 H, ArH), 7.81 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.86-8.01 (m, 16 H, ArH),
3
13
8.43 (d, JH, H = 1.5 Hz, 4 H, ArH) ppm; C NMR (75.47 MHz, CDCl3): = 14.17,
22.69, 26.58, 29.13, 29.17, 29.87, 31.79, 43.59, 122.82, 128.13, 128.15, 128.25, 129.70,
129.84, 129.86, 130.02, 130.91, 131.94, 132.33, 132.75, 135.60, 135.62, 137.27, 139.94,
140.05, 142.69 ppm; MS (ESI pos., CH3OH/CH2Cl2): m/z = 1377.18 [M+Na]+ calcd
1
16
monoisotopic peak (12C66 H5814N4 O1432S7Na) 1377.19; 1393.11 [M+K]+ calcd
monoisotopic peak (12C66 H5814N4 O1432S7K) 1393.16; elemental analysis calcd (%) for
1
16
S5

C66H58N4O14S7 (1355.64): C 58.47, H 4.31, N 4.13, S 16.56; found C 58.73, H 4.22, N
4.01, S 16.82.
Compound 9b: (Rf = 0.78, silica gel, CH2Cl2); yield 1.0 g (16%); m.p. 132-135 °C; 1H
3
NMR (500 MHz, CDCl3): = 0.81 (t, JH, H = 6.9 Hz, 3 H, CH3), 1.19 (m, 10 H, CH2),
1.67 (m, 2H, CH2), 3.69 (m, 2 H, CH2), 7.11 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.24 (d, 3JH, H
= 8.7 Hz, 4 H, ArH), 7.57-7.69 (m, 10 H, ArH), 7.75 (d, 3JH, H = 8.7 Hz, 4 H, ArH), 7.86-
3
3
8.07 (m, 22 H, ArH), 8.44 (d, JH, H = 1.5 Hz, 4 H, ArH), 8.56 (d, JH, H = 1.5 Hz, 1 H,
ArH) ppm; 13C NMR (75.47 MHz, CDCl3): = 14.16, 22.65, 26.63, 28.99, 29.13, 30.03,
31.73, 50.06, 122.64, 122.81, 127.94, 128.01, 128.12, 128.46, 129.51, 129.75, 129.83,
129.97, 130.38, 130.90, 131.91, 131.96, 132.27, 132.79, 135.46, 135.58, 136.44, 138.27,
139.86, 140.07, 142.33 ppm; MS (ESI pos., CH3OH): m/z = 1583.05 [M+K]+ calcd
1
16
monoisotopic peak (12C76 H6414N4 O1632S8K) 1583.17; 1567.18 [M+Na]+ calcd
monoisotopic peak (12C76 H6414N4 O1632S8Na) 1567.20; elemental analysis calcd (%) for
C76H64N4O16S8 (1545.86): C 59.05, H 4.17, N 3.62, S 16.59; found C 59.26, H 4.21, N
3.68, S 16.56.
1
16
Compound 9c: 2 g of 9a were used in the reaction. Purified by column
chromatography (Rf = 0.73, silica gel, CH2Cl2); yield 1.52 g (68%); m.p. 149-151 °C; 1H
3
NMR (500 MHz, CDCl3): = 0.83 (t, JH, H = 6.9 Hz, 3 H, CH3), 1.19 (m, 10 H, CH2),
1.67 (br. 2H, CH2), 3.71 (m, 2 H, CH2), 7.15 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.26 (d, 3JH, H
= 8.7 Hz, 4 H, ArH), 7.60-7.70 (m, 8 H, ArH), 7.77 (d, 3JH, H = 8.7 Hz, 4 H, ArH), 7.87-
3
3
8.04 (m, 18 H, ArH), 8.17 (d, JH, H = 9.0 Hz, 2 H, ArH), 8.36 (d, JH, H = 9.0 Hz, 2 H,
3
ArH), 8.44 (d, JH, H = 1.5 Hz, 4 H, ArH) ppm; MS (ESI pos., CH3OH): m/z = 1578.16
[M+K]+ calcd monoisotopic peak (12C72 H6114N5 O1832S8K) 1578.14; 1562.16 [M+Na]+
1
16
calcd monoisotopic peak (12C72 H6114N5 O1832S8Na) 1562.17; elemental analysis calcd
(%) for C72H61N5O18S8 (1540.80): C 56.12, H 3.99, N 4.55, S 16.65; found C 55.98, H
4.20, N 4.41, S 16.62.
1
16
Compound 9d: M.p. 137-139 °C; 1H NMR (500 MHz, CDCl3): = 0.85 (t, 3JH, H = 6.9
Hz, 3 H, CH3), 1.21 (m, 10 H, CH2), 1.69 (br. 2H, CH2)3, 3.63 (m, 2 H, CH2), 6.75 (br. 2
3
H, NH2), 7.12 (d, JH, H = 8.7 Hz, 2 H, ArH), 7.27 (d, JH, H = 8.7 Hz, 4 H, ArH), 7.61-
3
7.70 (m, 8 H, ArH), 7.77 (d, JH, H = 8.7 Hz, 4 H, ArH), 7.88-8.01 (m, 18 H, ArH), 8.46
3
(d, JH, H = 1.5 Hz, 4 H, ArH) ppm; MS (ESI pos., CH3OH/CH2Cl2): m/z = 1532.19
1
16
[M+Na]+ calcd monoisotopic peak (12C72 H6314N5 O1832S8Na) 1532.19; 1548.22 [M+K]+
1
16
calcd monoisotopic peak (12C72 H6314N5 O1832S8K) 1548.17.
Compound 10a: 850 mg of 9d were used in the reaction. Purified by column
chromatography (Rf = 0.25, silica gel, CH2Cl2); yield 750 mg (72%); m.p. 189-191 °C;
1H NMR (500 MHz, CDCl3): = 0.84 (t, 3JH, H = 6.9 Hz, 3 H, CH3), 1.24 (m, 10 H, CH2),
1.73 (br. 2H, CH2), 3.73 (m, 2 H, CH2), 7.17 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.22 (d, 3JH, H
3
= 8.7 Hz, 2 H, ArH), 7.28 (d, JH, H = 8.7 Hz, 4 H, ArH), 7.62-7.71 (m, 8 H, ArH), 7.77
3
3
(d, JH, H = 8.7 Hz, 4 H, ArH), 7.88-8.01 (m, 18 H, ArH), 8.13 (d, JH, H = 9.0 Hz, 4 H,
3
3
ArH), 8.39 (d, JH, H = 9.0 Hz, 4 H, ArH), 8.46 (d, JH, H = 1.5 Hz, 4 H, ArH) ppm; MS
(ESI pos., CH3OH/CH2Cl2): m/z = 1902.16 [M+Na]+ calcd monoisotopic peak
(12C84 H6914N7 O24 S10Na) 1902.15; 1918.04 [M+K]+ calcd monoisotopic peak
1
16
32
S6

1
16
32
(12C84 H6914N7 O24 S10K) 1918.12; elemental analysis calcd (%) for C84H69N7O24S10
(1881.13): C 53.63, H 3.70, N 5.21, S 17.05; found C 53.78, H 3.80, N 5.33, S 16.90.
1
3
Compound 10b: M.p. 140-142 °C; H NMR (500 MHz, CDCl3): = 0.85 (t, JH, H
=
6.9 Hz, 3 H, CH3), 1.23 (m, 10 H, CH2), 1.71 (br. 2H, CH2), 3.65 (m, 2 H, CH2), 6.64 (br.
3
3
4 H, NH2), 7.14 (d, JH, H = 8.7 Hz, 2 H, ArH), 7.22 (d, JH, H = 8.7 Hz, 2 H, ArH), 7.27
3
3
(d, JH, H = 8.7 Hz, 4 H, ArH), 7.61-7.71 (m, 8 H, ArH), 7.77 (d, JH, H = 8.7 Hz, 4 H,
ArH), 7.87-8.01 (m, 20 H, ArH), 8.46 (d, 3JH, H = 1.5 Hz, 4 H, ArH) ppm; MS (ESI pos.,
CH3OH/CH2Cl2):
m/z
=
1842.19 [M+Na]+ calcd monoisotopic peak
1
16
32
(12C84 H7314N716O20 S10Na) 1842.20; 1858.19 [M+K]+ calcd monoisotopic peak
1
32
(12C84 H7314N7 O20 S10K) 1858.18.
Compound 11: 430 mg of 13b were used in the reaction. Purified by column
chromatography (Rf = 0.19, silica gel, CH2Cl2); yield 312 mg (54%); m.p. 214-215 °C;
1H NMR (500 MHz, CDCl3): = 0.84 (t, 3JH, H = 6.9 Hz, 3 H, CH3), 1.22 (m, 10 H, CH2),
1.78 (br. 2H, CH2), 3.73 (m, 2 H, CH2), 7.15 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.17 (d, 3JH, H
3
3
= 8.7 Hz, 2 H, ArH), 7.20 (d, JH, H = 8.7 Hz, 4 H, ArH), 7.23 (d, JH, H = 8.7 Hz, 4 H,
3
ArH), 7.58-7.68 (m, 8 H, ArH), 7.73 (d, JH, H = 8.7 Hz, 4 H, ArH), 7.80-7.95 (m, 24 H,
ArH), 8.08 (d, 3JH, H = 9.0 Hz, 8 H, ArH), 8.37 (d, 3JH, H = 9.0 Hz, 8 H, ArH), 8.41 (d, 3JH,
= 1.5 Hz, 4 H, ArH) ppm; MS (ESI pos., CH3OH/CH2Cl2): m/z = 2598.20 [M+K]+
H
1
14
16
32
calcd monoisotopic peak (12C108 H85
N
36
O
14
S K) 2598.09; 2582.12 [M+Na]+ calcd
S Na) 2582.11; elemental analysis calcd (%)
11
32
36
14
1
14
16
monoisotopic peak (12C108 H85
N
O
11
for C108H85N11O36S14 (2561.79): C 50.63, H 3.34, N 6.01, S 17.52; found C 50.38, H
3.16, N 5.93, S 17.38.
Compound 12a: 3 g of 5a were used in the reaction. Recrystallized from methanol;
1
3
yield 4.2 g (84%); m.p. 74-78 °C; H NMR (300 MHz, CDCl3): = 0.91 (t, JH, H = 6.9
3
Hz, 3 H, CH3), 1.26 (s, 10 H, CH2), 1.69 (br. 2 H, CH2), 3.74 (t, JH, H = 7.5 Hz, 2 H,
CH2), 7.76 (d, 3JH, H = 8.4 Hz, 2 H, ArH), 7.96 (d, 3JH, H = 8.4 Hz, 2 H, ArH), 8.27 (d, 3JH,
3
13
= 9.0 Hz, 2 H, ArH), 8.44 (d, JH, H = 9.0 Hz, 2 H, ArH) ppm; C NMR (75.47 MHz,
H
CDCl3): = 14.08, 22.60, 26.48, 28.90, 29.08, 29.89, 31.68, 50.10, 124.34, 129.55,
129.67, 129.77, 132.60, 138.48, 145.55, 150.64 ppm; MS (EI, 80 eV): m/z = 534.03 [M]+,
434.92 [M – C7H15]+, 348.05 [M – p-NO2C6H4SO2]+, 313.12 [M – p-BrC6H4SO2]+,
220.91 [M – p-NO2C6H4SO2NC8H17]+, 185.99 [M – p-BrC6H4SO2NC8H17]+; elemental
analysis calcd (%) for C20H25BrN2O6S2 (533.46): C 45.03, H 4.72, Br 14.98, N 5.25, S
12.02; found C 44.93, H 4.65, Br 15.11, N 5.24, S 12.23.
Compound 12b: Yield 2.7 g (96%); m.p. 73-77 °C; 1H NMR (300 MHz, (CD3)2CO):
= 0.89 (t, 3JH, H = 6.9 Hz, 3 H, CH3), 1.25 (s, 10 H, CH2), 1.66 (br. 2 H, CH2), 3.67 (t, 3JH,
H = 7.5 Hz, 2 H, CH2), 5.81 (s, 2 H, NH2), 6.76 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.64 (d, 3JH,
3
= 8.7 Hz, 2 H, ArH), 7.81 (d, JH, H = 8.4 Hz, 2 H, ArH), 7.87 (d, 3JH, H = 8.4 Hz, 2 H,
H
13
ArH) ppm; C NMR (75.47 MHz, (CD3)2CO): = 14.45, 23.36, 27.26, 27.31, 29.17,
29.89, 32.55, 50.05, 125.85, 128.89, 129.74, 130.71, 131.42, 133.16, 141.10, 155.07
ppm; MS (EI, 80 eV): m/z = 504.06 [M]+, 346.05 [M – p-NH2C6H4SO2NC8H17]+, 283.15
[M – p-BrC6H4SO2NC8H17]+, 220.91 [M – p-NH2C6H4SO2NC8H17]+, 156.01 [M – p-
BrC6H4SO2NC8H17]+.
S7

Compound 13a: 2.9
g
of 12b were used. Recrystallized from
1
dichloromethane/methanol; yield 3.4 g (68%); m.p. 173-174 °C. H NMR (300 MHz,
3
CDCl3): = 0.91 (t, JH, H = 6.9 Hz, 3 H, CH3), 1.27 (s, 10 H, CH2), 1.70 (br. 2H, CH2),
3.73 (t, 3JH, H = 7.6 Hz, 2 H, CH2), 7.28 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.76 (d, 3JH, H = 8.4
3
3
Hz, 2 H, ArH), 7.94 (d, JH, H = 8.4 Hz, 2 H, ArH), 8.14 (d, JH, H = 8.7 Hz, 2 H, ArH),
3
3
13
8.19 (d, JH, H = 9.0 Hz, 4 H, ArH), 8.48 (d, JH, H = 9.0 Hz, 4 H, ArH) ppm; C NMR
(75.47 MHz, (CD3)2SO): = 13.90, 22.02, 25.75, 28.30, 28.48, 29.32, 31.11, 49.60,
125.15, 128.88, 129.42, 129.66, 130.04, 132.69, 132.75, 137.40, 138.10, 141.38, 142.54,
151.10 ppm; MS (EI, 80 eV): m/z = 874.02 [M]+, 774.90 [M –C7H15]+, 689.05 [M – p-
NO2C6H4SO2]+, 653.13 [M – p-BrC6H4SO2]+, 525.99 [M –p-BrC6H4SO2NC8H17]+;
elemental analysis calcd (%) for C32H33BrN4O12S4 (873.79): C 43.99, H 3.81, Br 9.14, N
6.41, S 14.68; found C 43.79, H 4.00, Br 8.89, N 6.30, S 14.74.
Compound 13b: 2.2
g
of 12b were used. Recrystallized from
1
dichloromethane/methanol; yield 3.0 g (84%); m.p. 142-144 °C; H NMR (300 MHz,
3
CDCl3): = 0.91 (t, JH, H = 6.9 Hz, 3 H, CH3), 1.28 (s, 10 H, CH2), 1.69 (br. 2H, CH2),
2.52 (s, 6 H, CH3), 3.70 (t, 3JH, H = 7.5 Hz, 2 H, CH2), 7.25 (d, 3JH, H = 8.7 Hz, 2 H, ArH),
3
3
3
7.39 (d, JH, H = 7.5 Hz, 4 H, ArH), 7.75 (d, JH, H = 8.4 Hz, 2 H, ArH), 7.84 (d, JH, H
=
7.5 Hz, 4 H, ArH), 7.88 (d, 3JH, H = 8.4 Hz, 2 H, ArH), 8.04 (d, 3JH, H = 8.7 Hz, 2 H, ArH)
ppm; 13C NMR (75.47 MHz, CDCl3): = 14.19, 21.86, 22.70, 26.63, 29.02, 29.20, 29.99,
31.80, 50.03, 128.70, 129.19, 129.35, 129.43, 129.76, 129.94, 132.46, 132.60, 136.15,
138.93, 139.44, 141.22 ppm; MS (EI, 80 eV): m/z = 810.08 [M]+, 658.06 [M –p-
CH3C6H4SO2]+, 591.16 [M – p-BrC6H4SO2]+, 464.03 [M –p-BrC6H4SO2NC8H17]+;
elemental analysis calcd (%) for C34H39BrN2O8S4 (811.85): C 50.30, H 4.84, Br 9.84, N
3.45, S 15.80; found C 50.34, H 4.86, Br 9.93, N 3.43, S 15.96.
Compound 14: Yield 1.1 g (91%); m.p. 79-83 °C; 1H NMR (300 MHz, CD3OD):
=
0.93 (t, 3JH, H = 7.0 Hz, 3 H, CH3), 1.27 (s, 10 H, CH2), 1.62 (br. 2H, CH2), 3.54 (m, 2 H,
CH2), 6.68 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.28 (d, 3JH, H = 8.4 Hz, 2 H, ArH), 7.60 (d, 3JH,
= 8.4 Hz, 2 H, ArH), 7.75 (m, 6 H, ArH) ppm; MS (EI, 80 eV): m/z = 659.06 [M]+,
H
439.16 [M – p-BrC6H4SO2]+, 311.01 [M – p- NO2C6H4SO2NC8H17]+.
Compound 15a: 1 g of 14 was used in the reaction. Recrystallized from
1
dichloromethane/methanol; yield 1.29 g (70%), m.p. 202-204 °C; H NMR (500 MHz,
3
CDCl3): = 0.90 (t, JH, H = 6.9 Hz, 3 H, CH3), 1.26 (s, 10 H, CH2), 1.70 (br. 2H, CH2),
3
3
3.73 (m, 2 H, CH2), 7.28 (d, JH, H = 8.7 Hz, 2 H, ArH), 7.30 (d, JH, H = 8.7 Hz, 2 H,
ArH), 7.77 (d, 3JH, H = 8.4 Hz, 2 H, ArH), 7.94 (d, 3JH, H = 8.4 Hz, 2 H, ArH), 8.02 (d, 3JH,
H = 8.7 Hz, 2 H, ArH), 8.12 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 8.20, (d, 3JH, H = 9.0 Hz, 2 H,
ArH), 8.21 (d, 3JH, H = 9.0 Hz, 4 H, ArH), 8.49 (d, 3JH, H = 9.0 Hz, 2 H, ArH), 8.51 (d, 3JH,
= 9.0 Hz, 4 H, ArH) ppm; MS (ESI pos., CH3OH/CH2Cl2): m/z = 1250.96 [M+K]+
H
1
16
calcd monoisotopic peak (12C44 H4179Br14N6 O1832S6K) 1250.96; 1234.98 [M+Na]+ calcd
1
16
monoisotopic peak (12C44 H4179Br14N6 O1832S6Na) 1234.99; elemental analysis calcd (%)
for C44H41BrN6O18S6 (1214.12): C 43.53, H 3.40, Br 6.58, N 6.92, S 15.85; found C
43.79, H 3.65, Br 6.55, N 7.11, S 15.81.
S8

Compound 15b: 0.9 g of 14 was used in the reaction. Recrystallized from
1
dichloromethane/methanol; yield 1.14 g (77%); m.p. 208-211 °C; H NMR (500 MHz,
3
CDCl3): = 0.90 (t, JH, H = 6.9 Hz, 3 H, CH3), 1.27 (s, 10 H, CH2), 1.70 (br. 2H, CH2),
2.52 (s, 9 H, CH3), 3.71 (m, 2 H, CH2), 7.20 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.22 (d, 3JH, H
3
3
= 8.7 Hz, 2 H, ArH), 7.37 (d, JH, H = 8.0 Hz, 6 H, ArH), 7.71 (d, JH, H = 8.0 Hz, 2 H,
ArH), 7.75 (d, 3JH, H = 8.4 Hz, 2 H, ArH), 7.82 (d, 3JH, H = 8.0 Hz, 4 H, ArH), 7.86 (d, 3JH,
= 8.4 Hz, 2 H, ArH), 7.91 (d, JH, H = 8.7 Hz, 2 H, ArH), 8.03 (d, 3JH, H = 8.7 Hz, 2 H,
3
H
ArH) ppm; 13C NMR (75.47 MHz, CDCl3): = 14.20, 21.89, 21.92, 22.72, 26.65, 29.04,
29.22, 31.81, 50.08, 128.75, 129.36, 129.53, 129.61, 129.80, 130.01, 130.10, 132.42,
132.58, 132.65, 135.72, 136.15, 138.89, 138.98, 139.88, 140.37, 141.64, 144.38, 145.81,
146.12 ppm. MS (ESI pos., CH3OH/CH2Cl2): m/z = 1158.05 [M+K]+ calcd monoisotopic
peak (12C47 H5079Br14N3 O1232S6K) 1158.05; 1142.07 [M+Na]+ calcd monoisotopic peak
1
16
(12C47 H5079Br14N3 O1232S6Na) 1142.08; elemental analysis calcd (%) for
C47H50BrN3O12S6 (1121.21): C 50.35, H 4.49, Br 7.13, N 3.75, S 17.16; found C 50.06, H
4.53, Br 7.30, N 3.69, S 17.30.
1
16
1
3
Compound 16: M.p. 142-144 °C; H NMR (300 MHz, CD3OD): = 0.93 (t, JH, H
=
7.0 Hz, 3 H, CH3), 1.29 (s, 10 H, CH2), 1.66 (br. 2H, CH2), 3.78 (m, 2 H, CH2), 7.08 (d,
3JH, H = 8.8 Hz, 4 H, ArH), 7.31 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.67 (d, 3JH, H = 8.4 Hz, 2
H, ArH), 7.74 (d, 3JH, H = 8.8 Hz, 4 H, ArH), 7.95 (d, 3JH, H = 8.4 Hz, 2 H, ArH), 8.01 (d,
3JH, H = 8.7 Hz, 2 H, ArH) ppm; MS (EI, 80 eV): m/z = 814.07 [M]+.
Compound 17a: 1 g of 16 was used. Recrystallized from dichloromethane/methanol;
yield 1.4 g (74%); m.p. 267-269 °C; 1H NMR (500 MHz, (CD3)2SO): = 0.83 (t, 3JH, H
=
7.0 Hz, 3 H, CH3), 1.17 (s, 10 H, CH2), 1.62 (br. 2H, CH2), 3.77 (t, 3JH, H = 7.6 Hz, 2 H,
CH2), 7.44 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.50 (d, 3JH,3H = 8.7 Hz, 4 H, ArH), 7.70 (d, 3JH,
= 8.4 Hz, 2 H, ArH), 7.92 (m, 6 H, ArH), 8.09 (d, JH, H = 8.7 Hz, 2 H, ArH), 8.17 (d,
H
3
3JH, H = 9.0 Hz, 8 H, ArH), 8.53 (d, JH, H = 9.0 Hz, 8 H, ArH) ppm; elemental analysis
calcd (%) for C56H49BrN8O24S8 (1554.45): C 43.27, H 3.18, Br 5.14, N 7.21, S 16.50;
found C 43.10, H 3.35, Br 5.19, N 7.52, S 16.74.
Compound 17b: 0.7 g of 16 was used. Purified by column chromatography (Rf = 0.39,
silica gel, CH2Cl2); yield 0.9 g (72%), m.p. 127-129 °C; 1H NMR (500 MHz, CDCl3): =
0.90 (t, 3JH, H = 7.0 Hz, 3 H, CH3), 1.26 (s, 10 H, CH2), 1.72 (br. 2 H, CH2), 2.50 (s, 12 H,
CH3), 3.72 (m, 2 H, CH2), 7.15 (d, 3JH, H = 8.8 Hz, 2 H, ArH), 7.20 (d, 3JH, H = 8.8 Hz, 4
H, ArH), 7.33 (d, 3JH, H = 8.0 Hz, 8 H, ArH), 7.70 (d, 3JH, H = 8.4 Hz, 2 H, ArH), 7.77 (d,
3JH, H = 8.7 Hz, 4 H, ArH), 7.78 (d, 3JH, H = 8.0 Hz, 8 H, ArH), 7.82 (d, 3JH, H = 8.4 Hz, 2
3
13
H, ArH), 8.02 (d, JH, H = 8.7 Hz, 2 H, ArH) ppm; C NMR (75.47 MHz, CDCl3):
=
14.22, 21.91, 22.74, 26.66, 29.05, 29.23, 30.11, 31.81, 50.16, 128.75, 129.49, 129.55,
129.62, 129.68, 129.85, 130.07, 132.40, 132.70, 136.12, 138.53, 139.72, 140.30, 142.05,
145.89 ppm; MS (ESI pos., CH3OH): m/z = 1467.18 [M+K]+ calcd monoisotopic peak
1
16
(12C60 H6179Br14N416O1632S8K) 1467.07; 1451.21 [M+Na]+ calcd monoisotopic peak
1
(12C60 H6179Br14N4 O1632S8Na) 1451.09; elemental analysis calcd (%) for
C60H61BrN4O16S8 (1430.57): C 50.37, H 4.30, Br 5.59, N 3.92, S 17.93; found C 50.26, H
4.42, Br 5.60, N 3.86, S 17.83.
S9

Compound 18: 1 g of 13b was used in the reaction. Recrystallized from
1
chloroform/methanol; yield 820 mg (86%), m.p. 173-175 °C; H NMR (500 MHz,
CDCl3): = 0.85 (t, 3JH, H = 7.0 Hz, 6 H, CH3), 1.24 (s, 20 H, CH2), 1.71 (br. 4 H, CH2),
3
3
2.47 (s, 12 H, CH3), 3.70 (t, JH, H = 7.5 Hz, 4 H, CH2), 7.21 (d, JH, H = 8.7 Hz, 4 H,
ArH), 7.34 (d, 3JH, H = 8.0 Hz, 8 H, ArH), 7.74 (s, 4 H, ArH), 7.79 (d, 3JH, H = 8.0 Hz, 8 H,
ArH), 7.81 (d, 3JH, H = 8.7 Hz, 4 H, ArH), 8.03 (d, 3JH, H = 8.5 Hz, 4 H, ArH), 8.05 (d, 3JH,
13
= 8.5 Hz, 4 H, ArH) ppm; C NMR (75.47 MHz, CDCl3): = 14.22, 21.91, 22.75,
H
26.74, 29.13, 29.27, 29.85, 30.20, 31.86, 50.06, 127.82, 128.27, 128.76, 128.97, 129.25,
129.98, 132.49, 136.23, 138.86, 139.39, 139.45, 139.66, 141.45, 145.72 ppm; MS (ESI
pos.,
CH3OH):
m/z
=
1577.30
[M+K]+ calcd
monoisotopic
peak
1
16
(12C74 H8214N416O1632S8K) 1577.31; 1561.33 [M+Na]+ calcd monoisotopic peak
(12C74 H8214N4 O1632S8Na) 1561.34; elemental analysis calcd (%) for C74H82N4O16S8
1
(1539.98): C 57.71, H 5.37, N 3.64, S 16.66; found C 57.64, H 5.09, N 3.62, S 16.89.
Compound 19: 1 g of 15b was used in the reaction. Recrystallized from
1
chloroform/methanol; yield 730 mg (76%), m.p. 147-149 °C; H NMR (500 MHz,
CDCl3): = 0.87 (t, 3JH, H = 7.0 Hz, 6 H, CH3), 1.26 (s, 20 H, CH2), 1.71 (br. 4 H, CH2),
3
3
2.47 (s, 18 H, CH3), 3.71 (t, JH, H = 7.5 Hz, 4 H, CH2), 7.20 (d, JH, H = 8.7 Hz, 4 H,
3
3
ArH), 7.21 (d, JH, H = 8.7 Hz, 4 H, ArH), 7.36 (d, JH, H = 8.0 Hz, 12 H, ArH), 7.73 (d,
3JH, H = 8.7 Hz, 4 H, ArH), 7.74 (s, 4 H, ArH), 7.80 (d, 3JH, H = 8.0 Hz, 12 H, ArH), 7.90
(d, 3JH, H = 8.7 Hz, 4 H, ArH), 8.04 (d, 3JH, H = 8.5 Hz, 4 H, ArH), 8.06 (d, 3JH, H = 8.5 Hz,
13
4 H, ArH) ppm; C NMR (75.47 MHz, CDCl3): = 14.21, 21.90, 22.73, 26.72, 29.09,
29.25, 29.60, 30.14, 31.84, 50.06, 127.83, 128.27, 128.76, 128.99, 129.40, 129.62,
130.02, 130.11, 132.41, 135.75, 136.15, 138.75, 138.90, 139.42, 139.88, 140.39, 141.83,
145.82, 146.03, 146.11 ppm; MS (ESI pos., CH3OH/CH2Cl2): m/z = 2195.31 [M+K]+
1
16
32
calcd monoisotopic peak (12C100 H10414N6 O24 S12K) 2195.34; 2179.36 [M+Na]+ calcd
monoisotopic peak (12C100 H10414N6 O24 S12Na) 2179.36; elemental analysis calcd (%)
for C100H104N6O24S12 (2158.70): C 55.64, H 4.86, N 3.89, S 17.82; found C 55.78, H
4.85, N 3.87, S 17.95.
1
16
32
Compound 20: 800 mg of 17b were used in the reaction. Purified by column
chromatography (Rf = 0.33, silica gel, CH2Cl2); yield 600 mg (78%), m.p. 177-179 °C. 1H
3
NMR (500 MHz, CDCl3): = 0.87 (t, JH, H = 7.0 Hz, 6 H, CH3), 1.26 (s, 20 H, CH2),
1.72 (br. 4 H, CH2), 2.48 (s, 24 H, CH3), 3.72 (t, 3JH, H = 7.5 Hz, 4 H, CH2), 7.19 (d, 3JH, H
3
3
= 8.7 Hz, 4 H, ArH), 7.22 (d, JH, H = 8.7 Hz, 8 H, ArH), 7.36 (d, JH, H = 8.0 Hz, 16 H,
ArH), 7.77 (s, 4 H, ArH), 7.79 (d, 3JH, H = 8.7 Hz, 8 H, ArH), 7.80 (d, 3JH, H = 8.0 Hz, 16
3
H, ArH), 7.81 (d, JH, H = 8.7 Hz, 4 H, ArH), 8.07 (m, 8 H, ArH) ppm; 13C NMR (75.47
MHz, CDCl3): = 14.22, 21.91, 22.74, 26.73, 29.10, 29.26, 29.85, 30.18, 31.85, 127.86,
128.30, 128.76, 129.04, 129.59, 129.70, 132.39, 132.71, 136.13, 138.44, 139.37, 139.47,
139.74, 140.30, 142.25, 145.89 ppm. MS (ESI pos., CH3OH/CH2Cl2): m/z = 2813.93
1
16
32
[M+K]+ calcd monoisotopic peak (12C1216 H12614N8 O32 S16K) 2813.36; 2797.95
[M+Na]+ calcd monoisotopic peak (12C126 H12614N8 O32 S16Na) 2797.39; elemental
analysis calcd (%) for C126H126N8O32S16 (2777.42): C 54.49, H 4.57, N 4.03, S 18.47;
found C 54.61, H 4.70, N 3.81, S 18.27.
16
32
S10

Compound 21a: To a stirred solution of 4-methoxybenzylamine (1.05 g, 7.6 mmol) and
triethylamine (2mL) in dry dichloromethane (30 mL) a solution of benzene-1,3-disulfonyl
chloride (1 g, 3.6 mml) in dichloromethane (10 mL) was
O
S
O
S
added. The reaction mixture was stirred at room temperature
for 2 hs. Then the solvent was removed under reduced
pressure and the solid residue was recrystallized from
dichloromethane/methanol affording 1.60 g (93%) of
colorless crystalline solid. M.p. 158-160 °C; 1H NMR (300
O
O
HN
NH
O
O
21a
MHz, CDCl3): = 3.77 (s, 6 H, OCH3), 4.12 (d, 3JH, H = 6.0 Hz, 4 H, NCH2Ar), 5.19 (t,
3JH, H = 6.0 Hz, 2 H, NH), 6.78 (d, 3JH, H = 8.7 Hz, 4 H, ArH), 7.11 (d, 3JH, H = 8.7 Hz, 4
H, ArH), 7.58 (t, 3JH, H = 9.0 Hz, 1 H, ArH), 7.97 (d, 3JH, H = 9.0 Hz, 2 H, ArH), 8.28 (d,
3JH, H = 9.0 Hz, 2 H, ArH) ppm. EI-MS: m/z = 476.11 [M]+. C22H24N2O6S2 (476.57):
calcd. C 55.45, H 5.08, N 5.88, S 13.46; found C 55.46, H 4.98, N 5.69, S 13.40.
Compound 21: To a vigorously stirred suspension of 21a (1 g, 2.1 mmol) and Cs2CO3 (2
g) in acetonitrile (30 mL) a solution of tosyl chloride (1 g, 5.2 mmol) in acetonitrile (5
mL) was added. The reaction mixture was stirred at room
O
S
O
S
O
S
O
S
temperature for 2 hs. Then cesium salts were filtered through
a paper filter and the solvent was removed under reduced
pressure. The viscous residue was triturated with methanol
resulting in white powder, which was recrystallized from
O
O
O
O
N
N
O
O
21
methanol/dichloromethane. Yield 1.45 g (88%); m.p. 172-173 °C. 1H NMR (300 MHz,
CDCl3): = 2.45 (s, 3 H, CH3), 3.81 (s, 6 H, OCH3), 4.89 (s, 4 H, NCH2Ar), 6.80 (d, 3JH,
H = 8.0 Hz, 4 H, ArH), 7.30 (m, 8 H, ArH), 7.49 (t, 3JH, H = 8.4 Hz, 1 H, ArH), 7.71 (d,
3JH, H = 8.0 Hz, 4 H, ArH), 7.98 (d, 3JH, H = 8.4 Hz, 2 H, ArH), 8.14 (s, 1 H, ArH) ppm.
C36H36N2O10S4 (784.94): calcd. C 55.09, H 4.62, N 3.57, S 16.34; found C 55.06, H 4.54,
N 3.66, S 16.16.
Compound 22a: To a vigorously stirred suspension of 21a (2 g, 4.2 mmol) and Cs2CO3
(1.4 g, 4.2 mmol) in acetonitrile (30 mL) a solution of tosyl chloride (0.8 g, 4.2 mmol) in
acetonitrile (5 mL) was added dropwise. The reaction
O
S
O
S
O
S
mixture was stirred at room temperature for 2 hs. Then
cesium salts were filtered through a paper filter and the
solvent was removed under reduced pressure. The viscous
residue was subjected to a column chromatography (silica
O
O
O
HN
N
O
22a
O
gel, CH2Cl2, Rf = 0.18); yield 1.13 g (43%), m.p. 118-120 °C. 1H NMR (300 MHz,
CDCl3): = 2.45 (s, 3 H, CH3), 3.80 (s, 3 H, OCH3), 3.81 (s, 3 H, OCH3), 4.11 (d, 3JH, H
= 6.0 Hz, 2 H, NCH2Ar), 4.82 (t, 3JH, H = 6.0 Hz, 1 H, NH), 4.89 (s, 2 H, NCH2Ar), 6.78
(d, 3JH, H = 8.0 Hz, 2 H, ArH), 6.84 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.11 (d, 3JH, H = 8.7 Hz,
2 H, ArH), 7.34 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.39 (d, 3JH, H = 8.7 Hz, 2 H, ArH), 7.53
(m, 1 H, ArH), 7.80 (s, 1 H, ArH), 7.85 (d, 3JH, H = 8.0 Hz, 2 H, ArH), 7.94 (d, 3JH, H = 9.0
Hz, 1 H, ArH), 8.00 (d, 3JH, H = 9.0 Hz, 1 H, ArH) ppm. EI-MS: m/z = 630.12 [M]+.
C29H30N2O8S3 (630.75): calcd. C 55.22, H 4.79, N 4.44, S 15.25; found C 55.16, H 4.54,
N 4.65, S 15.17.
S11

Compound 22: To a vigorously stirred suspension of 22a (1 g, 1.6 mmol) and Cs2CO3 (2
g) in acetonitrile (30 mL) a solution of dansyl chloride (1 g, 3.7 mmol) in acetonitrile (5
mL) was added. The reaction mixture was stirred at room
N
temperature for 2 hs. Then cesium salts were filtered through
a paper filter and the solvent was removed under reduced
O
S
O
S
O
S
O
S
pressure. The solid residue was triturated with methanol
resulting in a yellow powder, which was recrystallized from
methanol/dichloromethane.Yield 1.17 g (85%), m.p. 165-166
°C. 1H NMR (300 MHz, CDCl3): = 2.45 (s, 3 H, CH3),
O
O
O
O
N
N
O
O
22
2.99 (s, 6 H, N(CH3)2), 3.78 (s, 6 H, OCH3), 4.89 (s, 2 H, NCH2Ar), 5.11 (s, 2 H,
NCH2Ar), 6.70 (d, 3JH, H = 6.0 Hz, 2 H, ArH), 6.78 (d, 3JH, H = 6.0 Hz, 2 H, ArH), 7.29-
8.38 (m, 18 H) ppm. MS (ESI pos., CH3OH/CH2Cl2): m/z = 902.175 [M+K]+, 886.201
[M+Na]+. C41H41N3O10S4 (864.04): calcd. C 56.99, H 4.78, N 4.86, S 14.84; found C
56.74, H 4.86, N 4.84, S 15.06.
S12

Cartesian coordinates of the B3LYP/6-31G(d) optimized structures
Format:
{Atom} {X} {Y} {Z}
-----------------------------------------------------------------------
Molecule A
-----------------------------------------------------------------------
---Begin of file---
N
O
O
C
H
H
S
O
O
N
H
C
H
C
C
H
C
H
C
C
H
C
H
H
H
-2.2176454
-2.6144012 -0.9110180 -3.7288878
0.1560670 -3.2647516
-2.3332476
3.1058199
3.3285020
2.8038185
0.4963691
-0.2134642 -0.9602238
0.6818705 1.4017380
1.9752502 -0.7219429
2.1869220 -1.3613381
1.2496946 -3.8143147
0.1492876
0.8819805
0.7088376
0.0086687
1.3694177
2.1551951
0.4776946
2.1073049
2.9465817
2.5279105
1.7462726
2.5121683
-1.4080929 -1.1070830 -1.3014963
-1.7919852 -2.0057018 -1.7679547
-1.5496258
-1.0896901
-1.2323850
-0.4570708
-0.0978975
-0.3010299
0.1208295 -1.9485346
1.3143698 -1.3998260
2.2428192 -1.9384825
1.2780588 -0.1576507
2.1860457
0.0532846
0.3136843
0.4917307
-0.7759709 -1.1386468 -0.0632019
-0.6586825 -2.0736971
4.3287541 -0.7087532
5.1660139 -0.0712096
4.6479865 -1.2799499
4.1179470 -1.4149631
0.4734811
1.0582631
0.7562924
1.9385790
0.2492877
---End of file---
Molecule B
-----------------------------------------------------------------------
---Begin of file---
N
H
H
C
H
H
S
O
O
N
H
C
H
C
C
H
C
-2.4221881
-2.9638988 -0.6290409 -4.0416349
0.1827011 -3.7756156
-2.8628398
2.7342276
2.9642345
2.4025044
0.1403892
-0.5764196 -0.9117646
0.3404511 1.4319587
1.6271220 -0.7214897
1.8587546 -1.2517310
-1.6075745 -1.0760877 -1.8655646
-1.9034987 -2.0032290 -2.3505283
-1.8545764
-1.4676392
-1.6541779
-0.8507641
1.0513546 -4.0484292
0.1305809
0.9296809
0.8325504
1.5497188
0.6111145 -0.0943236
0.0397236
1.6124699
2.4701384
2.0414672
1.3018293
2.1423768
0.1539861 -2.5103832
1.3453810 -1.8690738
2.3006941 -2.3536767
1.3100724 -0.6240500
S13

H
C
C
H
C
H
H
H
-0.5624409
-0.6094819
-0.9934994 -1.1115093 -0.6231651
-0.8154388 -2.0605776 -0.1282234
3.9655055 -0.7297902
4.7853923 -0.1074802
4.3154267 -1.2236637
2.2272875 -0.1218763
0.0828675 -0.0026940
0.5607806
0.1865388
1.4757367
3.7457810 -1.5030245 -0.1819391
---End of file---
Anion C''
-----------------------------------------------------------------------
---Begin of file---
C
H
C
H
H
C
H
C
C
H
C
S
O
O
N
H
C
H
H
S
O
O
N
C
H
C
C
H
C
H
C
C
H
C
H
H
H
0.4854319
1.5361750
-0.3255146
0.0984874
-2.3059146
-1.6788996
-3.2769273
-2.2301080
-1.4073492
0.5663717
-0.0511279
-2.1120234 -0.1728262 -2.6185694
-3.3921989 -0.0794324 -3.3376319
-1.0494073 -1.0461081 -3.1351211
-2.5500851 -0.5430583 -1.0166807
-3.2951191 -1.2367448 -1.0802953
3.3280623
3.2146223
2.6011986
1.8271301 -1.5841840
1.8633714 -3.0560900
1.4111463 -0.7796272
3.1219388 -1.0905087
-0.7982958 -2.0426709 -0.0606929
-1.0002392 -2.7779440 -0.8350778
-1.5171903 -0.8380259 -0.0465632
-1.2597074
-1.8397116
-0.2862991 -0.1289296
-0.0987440 0.5848671
0.4416524 -1.3232474
0.1755071 -2.2779007
0.7378234 -3.2062427
2.8786409 -1.9926354
2.9935220 -1.7428734
4.0024636 -2.1643280
4.9970897 -2.0523830
4.7314948 -2.6186333
3.8547123 -2.4795655
2.4390518 -2.8626504
2.5808668 -2.6157466
1.4674567 -2.4408311
0.7155313 -2.0162680
1.5986178 -2.1369184
0.3488573
0.8222647
0.8663688
2.2805356
3.2705073
1.6167818
3.0674080
3.2324754
4.2545540
2.3204168
0.1155026
1.0344918
0.9425145
0.9487833
1.9119002
2.7074523
1.8962281
0.9056430
0.9179350
1.7481067
1.6819832
2.4056833
0.7513911
4.7358619
4.9335225
5.4865026
4.8618348
0.6298785
1.7095370
0.1762007
0.1903729
---End of file---
Anion C'
-----------------------------------------------------------------------
---Begin of file---
C
H
-2.2886954
-1.9076670
3.8279279 -2.3768634
4.8405221 -2.2629118
S14

C
H
H
C
H
C
C
H
C
S
O
O
N
C
H
H
S
O
O
N
H
C
H
C
C
H
C
H
C
C
H
C
H
H
H
-3.6548868
-4.3416946
-5.2052784
-4.1402765
-3.6248299
-3.2628720
-1.8937977
-0.3392453
-1.4045833
-0.7587360
-1.3144130 -0.5529579 -4.3461573
0.5824419 0.7334417 -3.2835301
-0.9498073 -0.9095860 -1.9082622
3.6892410 -1.9136763
4.3213462 -1.1364893
3.4887012 -1.6049941
1.3919973 -0.6323283
0.3772047 -0.9337983
3.5767313 -2.2482137
4.3920919 -2.0318273
2.0744453 -2.2974343
2.2727621 -2.3965033
0.2089091 -2.7871435
1.2255134 -2.6703439
1.4826959 -2.7950818
2.9519762 -2.7640141
2.7803911 -2.6513015
0.1052334 -3.1491534
2.9191228
3.3729826
1.8876223
3.5613177
4.5858465
3.7088619
3.5927880
4.5785833
0.3042466
0.0133989
2.2253629
0.5771689
2.3884230 -2.0310105
2.4822322 -2.2797674
-0.7199311 -1.6974071
-1.4355336 -2.4608606
-0.3510182 -0.7409419 -0.6946141
0.5860499
0.9177583
1.1003793
1.8075893
0.7158492 -0.6651307
-0.2058968 -1.6673317
-0.5119511 -2.4066119
4.4014000 -3.2648185
5.3611439 -3.1942486
4.6062625 -3.6017819
3.7881348 -4.0264777
0.2601113 -0.2953404
0.9899919 -1.0225797
0.2923635
1.0650128
0.9914266
1.2776375
1.9418062
1.5828146
2.3173763
2.9262917
2.4014333
3.9510057
2.4347159
---End of file---
Molecule C
-----------------------------------------------------------------------
---Begin of file---
C
H
C
H
H
C
H
C
C
H
C
S
O
O
N
H
C
-1.6537999
-1.0574963
-3.0439595
-3.5310048
-4.8970261
-3.8148998
-3.7859232
-3.1982771
-1.8044022
0.0562128
-1.0222364
-1.0017692
-1.6890061 -0.7548061 -4.0741903
0.4423706 0.2464410 -3.0681587
-1.4451957 -0.8060340 -1.6076617
-1.8592067 -1.6952987 -1.8723237
3.9305476 -1.4414019
4.0093995 -2.7856483
4.9170459 -2.7915008
4.0827891 -2.6912504
5.0511417 -2.6191598
2.9769795 -2.6237291
2.9159148 -2.6923657
0.7585995 -2.7945031
1.6706102 -2.7850379
1.6121416 -2.8662422
2.6860367 -2.9591706
2.7672567 -2.8766078
0.0180965 -3.0374414
2.7908370
S15

H
H
S
O
O
N
H
C
H
C
C
H
C
H
C
C
H
C
H
H
H
4.3585635 -0.6506035
3.6681213 -0.9861349
1.4153541 -0.9009287
0.5585706 -1.5822425
3.4206121
1.8297734
3.6464349
4.6232756
3.9004580
3.3707631
4.2475071
0.3926240
0.0423412
1.9206020
0.4553280
2.6886110 -1.9858971
2.8383626 -2.4859430
-0.7494952 -1.9674295
-1.2876524 -2.8447816
-0.7190631 -0.8060224 -0.4000995
-0.0293122
-0.0062816
0.6302457
1.1604178
0.3253963
1.2322080 -0.5342415
0.2876674
1.1593949
0.0571621
1.2826831
1.6502786
2.0578837
1.6197148
2.2339248
2.5748017
2.1201733
3.5250746
1.9175329
0.5958012 -0.8709384
-0.1023252 -1.9995027
-0.1358164 -2.8930829
4.9338680 -2.5709840
5.8495770 -2.1785968
5.2115970 -3.0434396
4.5198420 -3.3418372
---End of file---
Molecule D
-----------------------------------------------------------------------
---Begin of file---
C
H
C
H
H
C
H
C
C
H
C
S
O
O
S
O
O
N
C
H
H
S
O
O
N
H
C
H
C
C
H
4.1661008 -3.5624217
5.1443432 -3.6253329
3.2809332 -4.6406242
3.5734864 -5.5435654
1.3416676 -5.4100583
2.0241179 -4.5667194
0.6805025 -3.3411301 -0.8126790
1.6429441 -3.4116745 -0.3182459
2.5388199 -2.3410322 -0.3765656
4.4705242 -1.5492871
3.8017215 -2.3988375
2.0451727 -0.8668361 -1.2658161
3.2355718 -0.1762410 -1.7533076
0.9492213 -1.2260906 -2.1634124
0.8932358
1.3605757
0.9689880
1.4976974
0.4159350
0.3640548
0.1551463
0.2167024
2.2300797
1.4060610
3.5681818
1.3012496
1.2038309
1.3905699
0.6258361
0.9706237
2.1624023
1.0480155
0.1583152 -0.0645724
-6.3359456 -1.8933993
-7.2168958 -1.3082947
-6.2694566 -1.8541317
0.3584856
0.0588013
1.4474854
0.3794092
-4.6836911
-5.1737862
-5.0489961
0.2471612
1.2693060 -0.5560062
0.2849687 1.7980845
-5.0825932 -1.3099094 -0.1716451
-5.0753830 -1.2927414 -1.1921096
-0.8890196
-0.3876581
-0.1315428
0.8538219 -0.9227185
1.3510274 -1.7453813
0.1792689
0.0402930
1.1134151
1.8626941
-0.7586543 -0.4681383
-0.1528660 -0.9647193
S16

C
H
C
C
H
C
H
C
H
C
C
H
C
H
C
H
C
H
H
H
-2.1455014 -0.4469043
-2.6459345 -0.9283601
1.2197128
2.0528457
0.2422232
-2.8921843
-2.2792036
-2.8843167
1.4825946
0.8015289
1.4176627
0.7066126
2.3063400
3.2567385
3.9280203
3.3062613
4.0385927
2.4224385
2.4693410
0.2152719
0.8722013 -0.8242998
1.3998544 -1.5532545
5.0024765 -0.2022923
5.8022306
3.7800431
3.6129164
2.7670926
2.9443887 -0.9094840
2.1356982 -1.1733421
4.1722884 -1.5674283
4.3288256 -2.3539669
5.1967145 -1.2164875
6.1510497 -1.7336741
0.0734885
0.4672469
1.2685328
0.0996520
-6.4643377 -3.3353247 -0.1248308
-7.3738673 -3.7871696 0.2853827
-6.5322368 -3.3889754 -1.2183695
-5.6033112 -3.9309153 0.1940972
---End of file---
S17