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Supporting Information
Synthesis and Oligomerization of Fmoc/Boc-Protected
PNA Monomers of 2,6-Diaminopurine, 2-Aminopurine
and Thymine
André St. Amant and Robert H.E. Hudson*
Department of Chemistry, The University of Western Ontario, London, Ontario, Canada, N6A 5B7
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S2
Table of Contents
S2. Table of Contents
S3. General Remarks & mass spec of PNA1 & PNA2
S4. 1H NMR of 1 & 1H NMR of 1
S5. 1H NMR of 2 & 13C NMR of 2
S6. 1H NMR of 3 & 13C NMR of 3
S7. 1H NMR of 4 & 13C NMR of 4
S8. 1H NMR of 5 & 13C NMR of 5
S9. 1H NMR of 6 & 13C NMR of 6
S10. 1H NMR of 7 & 13C NMR of 7
S11. 1H NMR of 8 & 13C NMR of 8
S12. 1H NMR of 9 & 13C NMR of 9
S13. 1H NMR of 10 & 13C NMR of 10
S14. 1H NMR of 11a & 13C NMR of 11a
S15. 1H NMR of 12 & 13C NMR of 12
S16. 1H NMR of 13 & 13C NMR of 13
S17. 1H NMR of 14 & 13C NMR of 14
S18. HPLC chromatogram trace PNA1
S19. HPLC chromatogram trace PNA2
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S3
General Remarks. All chemicals were obtained from commercial sources and were of ACS reagent
grade or higher and were used without further purification. Solvents for solution-phase chemistry were
dried by passing through activated alumina columns. Flash column chromatography (FCC) was
performed on Merck Kieselgel 60, 230-400 mesh. Thin layer chromatography (TLC) was performed on
Merck Kieselgel 60 TLC plates. Chemical shifts are reported in parts per million (δ), were measured
from Tetramethylsilane (0 ppm) and are referenced to the solvent CDCl3 (7.26 ppm), DMSO-d6 (2.49
ppm), D2O (4.79 ppm) for 1H NMR and CDCl3 (77.0 ppm), DMSO-d6 (39.5 ppm) for
13C NMR.
Multiplicities are described as s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet) and br s
(broad singlet). Coupling constants (J) are reported in Hertz (Hz). Resonances due to restricted rotation
around the amide bond (rotamers) are reported as major (ma.) and minor (mi.). High resolution mass
spectra (HRMS) were obtained using electron impact (EI) or electrospray ionization (ESI).
PNA1. HRMS (ESI) calculated for C155H204N74O47: [M + 3H+] 1285.5361, Found 1285.8582; [M +
4H+] 964.404, Found 964.6530.
PNA2. HRMS (ESI) calculated for C125H161N67O35: [M + 3H+] 1054.4371, Found 1054.7417; [M +
4H+] 791.0798, Found 791.3110.
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S4
1H NMR (400 MHz, CDCl3) of 1
PROTON.esp
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
10.413.132.002.010.975.00
Chloroform-d
1.5
81.5
9
1.9
2
4.4
7
5.2
0
6.9
17.2
57.3
57.3
6
13C NMR (101 MHz, CDCl3) of 1
CARBON01.esp
220 200 180 160 140 120 100 80 60 40 20 0 -20
Chemical Shift (ppm)
0
0.25
0.50
0.75
1.00
Norm
alized Inte
nsity
M08(s)
M07(s)
M04(s)
M03(s)
M02(s)
M01(s)
M17(s)M14(s)
M12(s)
M11(s)
M10(s)
M16(s)
M15(s)
M13(s)
M09(s)
167.0
6
161.3
6
148.7
8147.5
8 139.6
5
134.5
5
128.4
5128.4
4128.1
9
110.4
7
86.5
7
77.3
276.6
967.5
2 48.5
5
27.1
9
12.0
6
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S5
1H NMR (400 MHz, DMSO-d6) of 2
PROTON.esp
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
9.082.851.931.00
DMSO-d6
1.4
91.7
9
2.4
9
3.1
6
4.4
1
7.6
4
13C NMR (101 MHz, DMSO-d6) of 2
CARBON01.esp
220 200 180 160 140 120 100 80 60 40 20 0 -20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
M10(s)
M09(s)M02(s)
M01(s)
M15(s)
M11(s)M14(s)
M13(s)
M12(s)
169.8
4 164.5
0
151.0
9
142.0
0141.8
2 108.3
8
49.1
348.6
9
40.1
339.9
239.7
239.3
039.0
9
27.7
5
11.9
6
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S6
1H NMR (400 MHz, DMSO-d6) of 3
Proton.esp
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
8.723.040.941.611.605.300.621.281.410.6210.791.952.01
DMSO-d6
1.1
41.1
61.1
81.4
11.4
61.4
81.7
81.9
82.4
92.4
93.2
53.2
63.3
33.4
34.1
34.3
14.3
34.7
55.1
25.2
0
7.2
87.3
07.3
27.3
47.3
57.3
9
7.6
57.6
77.8
67.8
8
13C NMR (101 MHz, CDCl3) of 3
Carbon.esp
220 200 180 160 140 120 100 80 60 40 20 0 -20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
Chloroform-d
170.7
4168.9
7166.8
8161.4
1161.3
2
148.6
4147.7
4
143.4
0140.7
9140.4
9134.7
1128.4
4128.3
4128.2
3127.7
7127.3
8
119.5
8
109.6
7109.4
7 86.3
286.2
277.3
2 77.0
076.6
867.4
366.8
266.3
966.2
559.9
5
48.5
346.7
438.7
7
27.5
526.9
7
20.5
9
13.8
011.8
6
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S7
1H NMR (400 MHz, DMSO-d6) of 4
2101.esp
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
8.450.052.981.941.987.581.591.750.950.860.754.511.030.561.811.920.64
DMSO-d6
1.4
51.4
8
1.7
7
2.4
92.4
92.7
22.8
83.1
6
3.9
54.2
24.5
2
7.3
17.4
07.6
67.8
67.8
87.9
4
13C NMR (151 MHz, CDCl3) of 4
CARBON_01
220 200 180 160 140 120 100 80 60 40 20 0 -20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
170.9
9170.6
0167.3
6164.5
4
156.4
7
151.1
2148.1
0143.9
4140.8
4
127.7
2
125.2
2120.1
6
108.2
6
86.1
6 65.6
5
47.8
9
46.8
739.7
839.6
439.5
139.3
739.2
331.3
727.0
8
11.9
7
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S8
1H NMR (400 MHz, CDCl3) of 5
1901.esp
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
37.359.361.00
Chloroform-d
7.2
5
1.6
81.4
31.4
1
13C NMR (101 MHz, CDCl3) of 5
CARBON01.ESP
220 200 180 160 140 120 100 80 60 40 20 0 -20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
0.8
9
27.5
727.7
127.8
1
41.9
376.6
977.0
077.3
283.2
283.8
787.2
6
127.8
2
143.8
3145.5
4149.6
9150.5
9
152.8
6153.7
0
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S9
1H NMR (400 MHz, DMSO-d6) of 6
0803.esp
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
39.961.000.70
Chloroform-d
0.0
5
1.1
11.1
31.1
31.1
51.1
81.1
91.4
01.4
21.4
41.5
61.5
91.6
31.6
41.6
51.6
63.4
43.4
63.4
73.4
93.7
03.7
2
7.2
5
8.3
38.3
5
11.2
211.2
2
13C NMR (101 MHz, CDCl3) of 6
CARBON01.ESP
220 200 180 160 140 120 100 80 60 40 20 0 -20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
27.5
827.7
427.8
0
76.7
977.0
077.2
183.3
984.3
0
109.9
2
145.3
4149.8
7150.8
0151.4
0
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S10
1H NMR (400 MHz, DMSO-d6) of 7
PROTON.esp
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
36.821.922.006.180.91
Chloroform-d
1.3
91.4
0
5.0
55.2
1
7.2
57.3
67.3
77.3
88.1
4
13C NMR (101 MHz, CDCl3) of 7
CARBON_01.ESP
220 200 180 160 140 120 100 80 60 40 20 0 -20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
27.5
627.6
727.7
6
44.1
444.2
752.8
9
67.9
476.6
877.0
077.3
283.1
883.6
8
126.7
4128.4
4128.6
7
145.7
8149.8
1150.6
4
154.1
9
167.0
0
175.9
7
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S11
1H NMR (400 MHz, DMSO-d6) of 8
PROTON.esp
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
35.942.001.04
DMSO-d6
8.6
3
5.0
5
3.4
03.3
8
2.4
91.4
01.4
0 1.3
71.3
51.3
31.2
71.2
61.2
61.2
5
13C NMR (101 MHz, MeOD-d4) of 8
CARBON_01.ESP
220 200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
28.0
2
31.0
848.3
048.5
148.7
248.9
449.1
549.3
649.5
8
84.8
985.3
7
128.1
2
149.7
4151.3
1152.1
6152.9
6155.9
0
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S12
1H NMR (400 MHz, DMSO-d6) of 9
PROTON
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
51.402.252.551.335.380.901.881.871.2913.972.301.991.05
8.5
08.4
9
7.8
67.6
7
7.3
4
5.4
35.2
4 5.1
14.5
14.3
64.1
7
3.5
63.3
43.2
0
2.5
12.5
02.5
02.3
7
1.3
51.3
0
13C NMR (101 MHz, CDCl3) of 9
CARBON.esp
220 200 180 160 140 120 100 80 60 40 20 0 -20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
Chloroform-d
14.3
5
22.8
627.9
028.0
2
31.8
0
47.4
449.1
549.3
7
66.7
467.6
0
83.5
683.9
884.0
1
120.2
5
128.0
2128.4
9128.8
9129.0
6
141.5
0143.8
5144.0
4150.1
9151.1
1152.1
8154.5
6
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S13
1H NMR (400 MHz, acetone-d6) of 10
PROTON_01.esp
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
35.990.731.821.041.050.930.811.690.770.930.270.383.891.951.980.94
1.3
8
1.3
91.4
01.4
1
2.0
32.0
32.0
42.0
5
3.3
0
3.7
44.1
84.3
04.3
24.4
24.4
45.3
05.4
3
7.3
07.3
27.3
87.4
07.6
77.6
97.8
27.8
47.8
58.3
6
13C NMR (101 MHz, acetone-d6) of 10
CARBON01.ESP
220 200 180 160 140 120 100 80 60 40 20 0 -20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
27.9
129.7
229.9
230.1
130.3
030.4
939.9
545.3
548.1
5
67.0
1
83.5
084.0
1
120.8
7
127.9
8128.5
7142.1
4145.1
0148.9
5151.0
0151.7
4152.7
9155.7
8157.5
3167.2
6167.8
8171.0
0
206.2
6
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S14
1H NMR (400 MHz, CDCl3) of 11a
1001.esp
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
19.202.072.155.181.00
Chloroform-d
1.4
21.5
8
5.0
55.2
2
7.2
57.3
57.3
77.3
78.1
9
13C NMR (101 MHz, CDCl3) of 11a
CARBON_01.ESP
220 200 180 160 140 120 100 80 60 40 20 0 -20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
27.6
8
44.4
5
68.0
5
76.6
877.0
083.5
9
128.4
7128.6
4128.7
7129.4
2134.2
4
146.4
2150.3
1
152.7
0
166.1
6
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S15
1H NMR (400 MHz, MeOH-d4) of 12
PROTON_01.esp
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
18.602.000.910.87
1.3
81.4
03.3
1
4.9
05.1
75.4
9
8.5
7
9.1
0
13C NMR (101 MHz, MeOH-d4) of 12
CARBON_01.esp
220 200 180 160 140 120 100 80 60 40 20 0
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
28.1
5
45.3
548.5
148.7
248.9
449.3
649.5
749.7
8
84.9
8
133.3
3
149.7
6152.2
4153.9
3154.3
9
170.0
1
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S16
1H NMR (400 MHz, CDCl3) of 13
PROTON_01.esp
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
17.260.650.531.720.380.561.131.251.020.430.841.190.541.191.830.608.902.542.630.840.330.96
9.1
1
8.0
57.7
37.7
17.5
87.3
97.3
77.2
7
5.7
65.2
55.1
94.9
94.9
34.4
94.4
74.4
14.3
94.0
84.0
73.6
33.4
82.7
9 1.5
81.4
3
13C NMR (101 MHz, CDCl3) of 13
CARBON_01
220 200 180 160 140 120 100 80 60 40 20 0 -20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
169.2
6
156.5
7152.7
0 150.9
5149.2
5
141.2
1
128.7
8128.6
1128.2
2127.7
3127.6
6127.0
1119.9
6109.9
2 83.3
077.3
276.6
9
67.3
9
49.1
947.1
4 29.6
127.7
727.2
7
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S17
1H NMR (400 MHz, CDCl3) of 14
PROTON_01.esp
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
20.611.631.351.350.831.013.730.960.990.500.120.260.395.222.442.380.370.561.00
1.3
71.4
01.4
3
2.7
7
3.3
63.5
44.0
14.1
74.1
94.2
14.8
55.3
06.0
56.8
37.1
77.2
37.2
47.2
57.2
77.3
37.7
17.7
38.1
08.2
89.0
99.1
2
13C NMR (101 MHz, CDCl3) of 14
CARBON_01
220 200 180 160 140 120 100 80 60 40 20 0 -20
Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Norm
alized Inte
nsity
171.5
6
156.8
9152.6
9150.9
6148.9
2143.6
4141.1
7131.3
8127.7
3127.0
7119.9
5 83.5
777.5
177.1
976.8
7
66.7
1
50.6
048.9
1 47.0
8
39.3
0
27.7
927.3
5
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S18
HPLC trace of crude PNA1
UPLC trace of purified PNA1
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
S19
HPLC trace of crude PNA2
UPLC trace of purified PNA2
Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2011
