J. Kania, L.-L. Gundersen
160 (14), 147 (30), 120 (20). HRMS (EI): C8H8N5 calcd. 175.0858, 6-Methoxy-7-(prop-1-en-1-yl)-7H-purine (5f): MeOH/CH2Cl2 (gra-
FULL PAPER
found 175.0854.
dient, 1:99 to 1:32) was used for flash chromatography; yield 84 mg
(87%), yellow solid, E/Z-mixture from Ru-mediated rearrangement
(Method C).
Ru-mediated rearrangement (Method C) gave 34 mg (38%), off-
white solid, E/Z-mixture. NMR spectroscopic data for the E-iso-
1
1
mer: H NMR (400 MHz, [D6]DMSO): δ = 1.84 (dd, J1 = 6.8, J2
Z-Isomer: H NMR (300 MHz, CDCl3): δ = 1.77 (dd, J1 = 6.9, J2
= 1.5 Hz, 3 H, CH3), 6.06–6.15 (m, 1 H, =CH), 6.94 (br. s, 2 H,
NH2), 7.32 (dd, J1 = 13.6, J2 = 1.6 Hz, 1 H, NCH=), 8.19 (s, 1 H,
2-H), 8.45 (s, 1 H, 8-H) ppm. 13C NMR (75 MHz, [D6]DMSO): δ
= 14.7 (CH3), 109.9 (C-5), 121.7 (=CH), 123.57 (NCH=), 143.1 (C-
8), 151.4 (C-6), 152.6 (C-2), 159.6 (C-4) ppm.
= 1.8 Hz, 3 H, CH3), 4.07 (s, 3 H, OCH3), 5.70–5.78 (m, 1 H,
=CH), 6.90 (dd, J1 = 8.4, J2 = 1.8 Hz, 1 H, NCH=), 8.05 (s, 1 H,
8-H), 8.58 (s, 1 H, 2-H) ppm. 13C NMR (75 MHz, CDCl3): δ =
12.5 (CH3), 54.0 (OCH3), 112.6 (C-5), 122.3 (=CH), 123.0
(NCH=), 144.7 (C-8), 152.4 (C-2), 157.4 (C-6), 161.1 (C-4) ppm.
1
E-isomer: H NMR (300 MHz, CDCl3): δ = 1.85 (dd, J1 = 6.9, J2
6-Chloro-7-(prop-1-en-1-yl)-7H-purine (5c): MeOH/CH2Cl2 (gradi-
ent, 1:199 to 1:99) was used for flash chromatography; yield 75 mg
(76%), pale yellow solid, E/Z-mixture from Ru-mediated re-
arrangement (Method C).
= 1.8 Hz, 3 H, CH3), 4.10 (s, 3 H, OCH3), 5.94–6.03 (m, 1 H,
=CH), 7.06 (dd, J1 = 14.1, J2 = 1.8 Hz, 1 H, NCH=), 8.19 (s, 1 H,
8-H), 8.58 (s, 1 H, 2-H) ppm. 13C NMR (75 MHz, CDCl3): δ =
15.0 (CH3), 54.1 (OCH3), 111.9 (C-5), 118.9 (=CH), 123.6
(NCH=), 142.2 (C-8), 152.1 (C-2), 157.2 (C-6), 161.4 (C-4) ppm.
MS (EI): m/z (%) = 190 (100) [M+], 175 (26), 162 (7), 148 (6), 136
(43). HRMS (EI): C9H10N4O calcd. 190.0855, found 190.0852.
1
Z-Isomer: H NMR (300 MHz, CDCl3): δ = 1.76 (dd, J1 = 7.2, J2
= 1.8 Hz, 3 H, CH3), 5.98–6.12 (m, 1 H, =CH), 6.96 (dd, J1 = 6.3,
J2 = 1.8 Hz, 1 H, NCH=), 8.19 (s, 1 H, 8-H), 8.89 (s, 1 H, 2-H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 12.4 (CH3), 122.0 (C-5),
122.1 (NCH=), 127.3 (=CH), 143.7 (C-6), 148.4 (C-8), 152.7 (C-2),
161.4 (C-4) ppm. E-isomer: 1H NMR (300 MHz, CDCl3): δ = 1.95
(dd, J1 = 8.1, J2 = 1.8 Hz, 3 H, CH3), 6.03–6.14 (m, 1 H, =CH),
7.20 (dd, J1 = 15.6, J2 = 3.3 Hz, 1 H, NCH=), 8.33 (s, 1 H, 8-H),
8.87 (s, 1 H, 2-H) ppm. 13C NMR (75 MHz, CDCl3): δ = 15.2
(CH3), 122.0 (C-5), 122.6 (NCH=), 124.3 (=CH), 143.5 (C-6), 146.7
(C-8), 152.5 (C-2), 161.7 (C-4) ppm. MS (EI): m/z (%) = 196/194
(33/100) [M+], 167 (8), 159 (15), 132 (13), 105 (15). HRMS (EI):
C8H7ClN4 calcd. 194.0359, found 194.0354.
6-Amino-9-(prop-1-en-1-yl)-9H-purine (6a): MeOH/CH2Cl2 (gradi-
ent, 1:49 to 1:24) was used for flash chromatography; yield 75 mg
(84%), off-white solid, E/Z-mixture from Ru-mediated rearrange-
ment (Method C).
Z-Isomer: 1H NMR (400 MHz, [D6]DMSO): δ = 1.76 (dd, J1
=
7.2, J2 = 1.2 Hz, 3 H, CH3), 5.74–5.81 (m, 1 H, =CH), 6.83 (dd,
J1 = 8.8, J2 = 1.6 Hz, 1 H, NCH=), 7.29 (br. s, 2 H, NH2), 8.15 (s,
1 H, 2-H), 8.24 (s, 1 H, 8-H) ppm. 13C NMR (100 MHz, [D6]-
DMSO): δ = 12.7 (CH3), 118.0 (C-5) 120.6 (NCH=), 121.3 (=CH),
139.7 (C-8) 149.3 (C-4), 153.0 (C-2), 156.0 (C-6) ppm. E-isomer:
2-Amino-6-chloro-7-(prop-1-en-1-yl)-7H-purine
(5d):
MeOH/
1H NMR (400 MHz, [D6]DMSO): δ = 1.82 (dd, J1 = 6.8, J2
=
CH2Cl2 (gradient, 1:199 to 1:32) was used for flash chromatog-
raphy; yield 65 mg (78%), pale yellow solid, E/Z-mixture from Ru-
mediated rearrangement (Method C).
0.8 Hz, 3 H, CH3), 6.49–6.57 (m, 1 H, =CH), 7.05 (dd, J1 = 14.4,
J2 = 1.6 Hz, 1 H, NCH=), 7.29 (br. s, 2 H, NH2), 8.17 (s, 1 H, 2-
H), 8.36 (s, 1 H, 8-H) ppm. 13C NMR (100 MHz, [D6]DMSO): δ
= 15.0 (CH3), 115.9 (=CH), 119.0 (C-5) 121.6 (NCH=), 138.4 (C-
8) 148.4 (C-4), 153.0 (C-2), 156.0 (C-6) ppm. MS (EI): m/z (%) =
175 (100) [M+], 160 (7), 148 (39), 135 (13), 120 (9). HRMS (EI):
C8H9N5 calcd. 175.0858, found 175.0853.
Z-Isomer: 1H NMR (400 MHz, [D6]DMSO): δ = 1.68 (dd, J1
=
6.8, J2 = 1.6 Hz, 3 H, CH3), 5.89–6.11 (m, 1 H, =CH), 6.68 (br. s,
2 H, NH2), 6.90 (dd, J1 = 8.0, J2 = 1.6 Hz, 1 H, NCH=), 8.38 (s,
1 H, 8-H) ppm. 13C NMR (100 MHz, [D6]DMSO): δ = 12.0 (CH3),
115.1 (C-5), 122.6 (NCH=), 124.8 (=CH), 142.7 (C-2), 148.7 (C-8),
160.1 (C-6), 163.6 (C-4) ppm. E-isomer: 1H NMR (400 MHz, [D6]-
DMSO): δ = 1.83 (dd, J1 = 6.8, J2 = 1.6 Hz, 3 H, CH3), 6.13–6.19
(m, 1 H, =CH), 6.68 (br. s, 2 H, NH2), 7.12 (dd, J1 = 13.6, J2 =
1.6 Hz, 1 H, NCH=), 8.56 (s, 1 H, 8-H) ppm. 13C NMR (100 MHz,
[D6]DMSO): δ = 14.8 (CH3), 114.3 (C-5), 120.9 (=CH), 122.6
(NCH=), 142.5 (C-2), 146.9 (C-8), 160.0 (C-6), 164.0 (C-4) ppm.
MS (EI): m/z (%) = 211/209 (33/100) [M+], 205 (11), 174 (29), 147
(9). HRMS (EI): C8H8ClN5 calcd. 209.0468, found 209.0461.
N6-Allyl-9-(prop-1-en-1-yl)-9H-purine (6b): MeOH/CH2Cl2 (gradi-
ent, 1:99 to 1:32) was used for flash chromatography; yield 44 mg
(89%), pale yellow solid, E/Z-mixture from K2CO3-mediated re-
arrangement (Method A).
1
Z-Isomer: H NMR (300 MHz, CDCl3): δ = 1.80 (dd, J1 = 7.2, J2
= 1.8 Hz, 3 H, CH3), 4.32 (br. s, 2 H, NCH2), 5.15 (d, J = 10.2 Hz,
1 H, HA in =CH2), 5.25 (d, J = 17.1 Hz, 1 H, HB in =CH2), 5.79–
5.84 (m, 1 H, =CH), 5.93–6.08 (m, 2 H, NH and CH=), 6.80 (dd,
J1 = 8.7, J2 = 1.8 Hz, 1 H, NCH=), 7.83 (s, 1 H, 8-H), 8.39 (s, 1
H, 2-H) ppm. 13C NMR (75 MHz, CDCl3): δ = 12.9 (CH3), 43.2
(NCH2), 116.4 (=CH2), 119.1 (C-5), 120.3 (NCH=), 123.2 (=CH),
134.4 (CH=), 139.1 (C-8), 149.2 (C-4), 153.6 (C-2), 154.8 (C-6)
6-Iodo-7-(prop-1-en-1-yl)-7H-purine (5e): The Ru-mediated re-
arrangement (Method C) was performed in 0.70 mmol scale.
MeOH/CH2Cl2 (gradient, 1:199 to 1:99) was used for flash
chromatography; yield 153 mg of compounds 5e and 5c (9:1) (ca.
73% yield of 5e), pale yellow solid, E/Z mixture.
ppm. E-isomer: 1H NMR (300 MHz, CDCl3): δ = 1.87 (dd, J1
=
6.9, J2 = 1.8 Hz, 3 H, CH3), 4.31 (br. s, 2 H, NCH2), 5.17 (d, J =
10.2 Hz, 1 H, HA in =CH2), 5.27 (d, J = 17.2 Hz, 1 H, HB in
=CH2), 5.92–6.05 (m, 2 H, NH and CH=), 6.25–6.37 (m, 1 H,
=CH), 6.95 (dd, J1 = 14.1, J2 = 1.5 Hz, 1 H, NCH=), 7.86 (s, 1 H,
8-H), 8.39 (s, 1 H, 2-H) ppm. 13C NMR (75 MHz, CDCl3): δ =
15.4 (CH3), 43.1 (NCH2), 116.4 (=CH2), 118.2 (=CH), 120.0 (C-
5), 121.2 (NCH=), 134.3 (CH=), 137.4 (C-8), 148.5 (C-4), 153.5
(C-2), 154.8 (C-6) ppm. MS (EI): m/z (%) = 215 (62) [M+], 200
(100), 188 (15), 174 (15), 160 (8). HRMS (EI): C11H13N5 calcd.
215.1171, found 215.1164.
1
Z-Isomer: H NMR (300 MHz, CDCl3): δ = 1.70 (dd, J1 = 7.2, J2
= 2.1 Hz, 3 H, CH3), 6.01–6.19 (m, 1 H, =CH), 7.06 (dd, J1 = 8.1,
J2 = 1.8 Hz, 1 H, NCH=), 8.16 (s, 1 H, 8-H), 8.74 (s, 1 H, 2-H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 12.6 (CH3), 108.8 (C-6),
121.5 (NCH=), 128.5 (=CH), 128.7 (C-5), 147.5 (C-8), 152.8 (C-2),
158.3 (C-4) ppm. E-isomer: 1H NMR (300 MHz, CDCl3): δ = 1.96
(dd, J1 = 6.9, J2 = 1.8 Hz, 3 H, CH3), 6.01–6.19 (m, 1 H, =CH),
7.32 (dd, J1 = 13.8, J2 = 1.8 Hz, 1 H, NCH=), 8.28 (s, 1 H, 8-H),
8.72 (s, 1 H, 2-H) ppm. 13C NMR (75 MHz, CDCl3): δ = 15.3
(CH3), 108.6 (C-6), 122.0 (NCH=), 126.0 (=CH), 128.2 (C-5), 146.7
(C-8), 152.6 (C-2), 158.8 (C-4) ppm. HRMS (EI) C8H7IN4 calcd. 6-Chloro-9-(prop-1-en-1-yl)-9H-purine (6c): MeOH/CH2Cl2 (gradi-
285.9715, found 285.9713. ent, 1:399 to 1:199) was used for flash chromatography; yield 85 mg
2014
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