The Journal of Organic Chemistry
Article
Hz, 1H, H-2′), 5.93−5.82 (m, 1H, CHCH2), 5.06 (dd, J = 1.5 and
3.3 Hz, 1H, CHCH), 5.01 (dd, J = 1.5 and 3.3 Hz, 1H, CHCH),
(CH(CH2)4), 32.2, 32.1, 25.9, 25.9 (4× CH2); HRMS (ESI-TOF)
m/z: calcd for C16H21N3O4 ([M + H]+), 320.1604, found 320.1607.
6-Cyclohexyl-9-β-D-ribofuranosyl-7-deazapurine (11l). Fol-
lowing a similar procedure to that used for the synthesis of 11a,
compound 11l was obtained starting from 10l (80 mg, 0.146 mmol)
and 20 mL of 7 N NH3 in MeOH (2.38 g, 14.0 mmol) after column
chromatography on silica gel (CH2Cl2/MeOH = 10:1, v/v) as a white
4.64 (dd, J3′,2′ = 5.2 Hz, J3′,4′ = 3.1 Hz, 1H, H-3′), 4.32 (ddd, J4′,3′
3.1 Hz, J4′,5′ = 3.3 Hz, J4′,5″ = 2.9 Hz, 1H, H-4′), 3.89−3.84 (dd, J5′,4′
=
=
3.3 Hz, Jgem = 11.9 Hz, 1H, H-5′), 3.79−3.74 (dd, J5″,4′ = 2.9 Hz, Jgem
= 11.9 Hz, 1H, H-5″), 3.14 (t, J = 7.1 Hz, 2H, CH2), 2.62−2.55 (m,
2H, CH2); 13C{1H} NMR (75 MHz, CD3OD) δ 162.0 (C-6), 150.0
(C-4), 149.6 (C-2), 136.6 (CHCH2), 127.0 (C-8), 118.4 (C-5),
114.2 (CHCH2), 99.4 (C-7), 88.8 (C-1′), 85.3 (C-2′), 73.9 (C-4′),
70.7 (C-3′), 61.6 (C-5′), 33.6 (CH2), 32.1 (CH2); HRMS (ESI-TOF)
m/z: calcd for C15H19N3O4 ([M + H]+), 306.1448, found 306.1446.
6-Isobutyl-9-β-D-ribofuranosyl-7-deazapurine (11i). Follow-
ing a similar procedure to that used for the synthesis of 11a,
compound 11i was obtained starting from 10i (80 mg, 0.146 mmol)
and 20 mL of 7 N NH3 in MeOH (2.38 g, 14.0 mmol) after column
chromatography on silica gel (CH2Cl2/MeOH = 10:1, v/v) as a white
1
semisolid (35 mg, 85%). H NMR (300 MHz, DMSO-d6) δ 8.69 (s,
1H, H-2), 7.78 (d, J = 3.8 Hz, 1H, H-8), 6.80 (d, J = 3.8 Hz, 1H, H-
7), 6.18 (d, J = 6.3 Hz, 1H, H-1′), 5.34 (d, JOH,2′ = 6.4 Hz, 1H, OH-
2′), 5.16 (d, JOH,3′ = 4.8 Hz, 1H, OH-3′), 5.09 (dd, JOH,5′ = 5.9 Hz,
J
OH,5″ = 4.8 Hz, 1H, OH-5′), 4.45 (ddd, J2′,1′ = 6.3 Hz, J2′,3′ = 5.6 Hz,
J2′,OH = 6.4 Hz, 1H, H-2′), 4.12 (ddd, J3′,2′ = 5.6 Hz, J3′,4′ = 4.1 Hz,
J3′,OH = 4.8 Hz, 1H, H-3′), 3.92 (ddd, J4′,3′ = 4.1 Hz, J4′,5′ = 3.9 Hz,
J
4′,5″ = 3.3 Hz, 1H, H-4′), 3.67−3.60 (ddd, J5′,4′ = 3.9 Hz, J5′,OH = 5.9
Hz, Jgem = 11.9 Hz, 1H, H-5′), 3.58−3.52 (ddd, J5″,4′ = 3.1 Hz, J5″,OH
=
1
semisolid (35 mg, 85%). H NMR (300 MHz, DMSO-d6) δ 8.69 (s,
5.0 Hz, Jgem = 11.9 Hz, 1H, H-5″), 3.11 (t, J = 11.4 Hz, 1H,
CH(CH2)5), 1.84−1.64 (m, 7H), 1.50−1.23 (m, 3H); 13C{1H} NMR
(75 MHz, DMSO-d6) δ 166.2 (C-6), 151.0 (C-2), 150.8 (C-4), 126.5
(C-8), 116.6 (C-5), 99.8 (C-7), 86.9 (C-1′), 85.2 (C-2′), 74.0 (C-4′),
70.7 (C-3′), 61.7 (C-5′), 43.0 (CH(CH2)5), 31.3, 31.3, 25.9, 25.7,
25.7 (5×CH2); HRMS (ESI-TOF) m/z: calcd for C17H23N3O4 ([M +
H]+), 334.1761, found 334.1762.
1H, H-2), 7.78 (d, J = 3.8 Hz, 1H, H-8), 6.76 (d, J = 3.8 Hz, 1H, H-
7), 6.19 (d, J = 6.3 Hz, 1H, H-1′), 5.36 (d, JOH,2′ = 6.4 Hz, 1H, OH-
2′), 5.18 (d, JOH,3′ = 4.8 Hz, 1H, OH-3′), 5.09 (dd, JOH,5′ = 5.8 Hz,
J
OH,5″ = 5.0 Hz, 1H, OH-5′), 4.45 (ddd, J2′,1′ = 6.3 Hz, J2′,3′ = 5.6 Hz,
J2′,OH = 6.4 Hz, 1H, H-2′), 4.12 (ddd, J3′,2′ = 5.6 Hz, J3′,4′ = 4.1 Hz,
J3′,OH = 4.8 Hz, 1H, H-3′), 3.92 (ddd, J4′,3′ = 4.1 Hz, J4′,5′ = 3.9 Hz,
J
4′,5″ = 3.3 Hz, 1H, H-4′), 3.67−3.60 (ddd, J5′,4′ = 3.9 Hz, J5′,OH = 5.8
6-(4-Isoproylphenyl)-9-β-D-ribofuranosyl-7-deazapurine
(11m). Following a similar procedure to that used for the synthesis of
11a, compound 11m was obtained starting from 10m (100 mg, 0.146
mmol) and 20 mL of 7 N NH3 in MeOH (2.38 g, 14.0 mmol) after
column chromatography on silica gel (CH2Cl2/MeOH = 10:1, v/v) as
Hz, Jgem = 11.9 Hz, 1H, H-5′), 3.58−3.51 (ddd, J5″,4′ = 3.1 Hz, J5″,OH
=
5.0 Hz, Jgem = 11.9 Hz, 1H, H-5″), 2.84 (d, J = 7.1 Hz, 2H, CH2CH),
2.27−2.18 (m, 1H, CH(CH3)2), 0.91 (d, J = 6.9 Hz, 6H, CH(CH3)2);
13C{1H} NMR (75 MHz, DMSO-d6) δ 161.9 (C-6), 150.9 (C-2),
150.6 (C-4), 126.6 (C-8), 118.3 (C-5), 100.1 (C-7), 96.9 (C-1′), 85.2
(C-2′), 74.0 (C-4′), 70.7 (C-3′), 61.7 (C-5′), 43.6 (CH2CH), 28.1
(CH(CH3)2), 22.6 (CH3), 22.5 (CH3); HRMS (ESI-TOF) m/z:
calcd for C15H21N3O4 ([M + H]+), 308.1604, found 308.1607.
6-Cycloproyl-9-β-D-ribofuranosyl-7-deazapurine (11j). Fol-
lowing a similar procedure to that used for the synthesis of 11a,
compound 11j was obtained starting from 10j (95 mg, 0.157 mmol)
and 20 mL of 7 N NH3 in MeOH (2.38 g, 14.0 mmol) after column
chromatography on silica gel (CH2Cl2/MeOH = 10:1, v/v) as a white
1
a white solid (40 mg, 74%). H NMR (300 MHz, DMSO-d6) δ 8.87
(s, 1H, H-2), 8.11 (d, J = 8.2 Hz, 2H, Ph-H), 7.95 (d, J = 3.8 Hz, 1H,
H-8), 7.47 (d, J = 8.2 Hz, 2H, Ph-H), 7.01 (d, J = 3.8 Hz, 1H, H-7),
6.28 (d, J = 6.1 Hz, 1H, H-1′), 5.40 (d, JOH,2′ = 6.3 Hz, 1H, OH-2′),
5.20 (d, JOH,3′ = 4.8 Hz, 1H, OH-3′), 5.11 (dd, JOH,5′ = 5.7 Hz, JOH,5″
4.8 Hz, 1H, OH-5′), 4.47 (ddd, J2′,1′ = 6.1 Hz, J2′,3′ = 5.6 Hz, J2′,OH
=
=
6.3 Hz, 1H, H-2′), 4.14 (ddd, J3′,2′ = 5.6 Hz, J3′,4′ = 4.1 Hz, J3′,OH = 4.8
Hz, 1H, H-3′), 3.94 (ddd, J4′,3′ = 4.1 Hz, J4′,5′ = 3.9 Hz, J4′,5″ = 3.3 Hz,
1H, H-4′), 3.69−3.62 (ddd, J5′,4′ = 3.9 Hz, J5′,OH = 5.7 Hz, Jgem = 11.9
1
Hz, 1H, H-5′), 3.60−3.54 (ddd, J5″,4′ = 3.1 Hz, J5″,OH = 4.6 Hz, Jgem
=
solid (40 mg, 88%). H NMR (300 MHz, DMSO-d6) δ 8.58 (s, 1H,
11.9 Hz, 1H, H-5″), 3.04−2.95 (m, 1H, CH(CH3)2), 1.27 (d, J = 6.9
Hz, 6H, 2× CH3); 13C{1H} NMR (75 MHz, DMSO-d6) δ 156.2 (C-
6), 152.1 (C-4), 151.1 (C-2), 150.9 (C-Ph), 135.3 (C-Ph), 128.8 (C-
Ph), 127.9 (C-Ph), 126.9 (C-8), 115.4 (C-5), 101.0 (C-7), 87.0 (C-
1′), 85.3 (C-4′), 74.2 (C-2′), 70.7 (C-3′), 61.7 (C-5′), 33.4
(CH(CH3)2), 23.8, 23.8 (CH(CH3)2); HRMS (ESI-TOF) m/z:
calcd for C20H23N3O4 ([M + H]+), 370.1761, found 370.1755.
6-(4-Methoxylphenyl)-9-β-D-ribofuranosyl-7-desazapurine
(11n). Following a similar procedure to that used for the synthesis of
11a, compound 11n was obtained starting from 10n (80 mg, 0.146
mmol) and 20 mL of 7 N NH3 in MeOH (2.38 g, 14.0 mmol) after
column chromatography on silica gel (CH2Cl2/MeOH = 10:1, v/v) as
H-2), 7.77 (d, J = 3.8 Hz, 1H, H-8), 6.88 (d, J = 3.8 Hz, 1H, H-7),
6.17 (d, J = 6.1 Hz, 1H, H-1′), 5.34 (d, JOH,2′ = 6.4 Hz, 1H, OH-2′),
5.17 (d, JOH,3′ = 4.6 Hz, 1H, OH-3′), 5.11 (dd, JOH,5′ = 5.7 Hz, JOH,5″
=
4.6 Hz, 1H, OH-5′), 4.43 (dd, J2′,1′ = 6.1 Hz, J2′,3′ = 5.6 Hz, 1H, H-
2′), 4.12 (dd, J3′,2′ = 5.6 Hz, J3′,4′ = 4.1 Hz, 1H, H-3′), 3.92 (ddd, J4′,3′
= 4.1 Hz, J4′,5′ = 3.9 Hz, J4′,5″ = 3.3 Hz, 1H, H-4′), 3.69−3.61 (ddd,
J5′,4′ = 3.9 Hz, J5′,OH = 5.7 Hz, Jgem = 11.9 Hz, 1H, H-5′), 3.59−3.53
(ddd, J5″,4′ = 3.1 Hz, J5″,OH = 4.6 Hz, Jgem = 11.9 Hz, 1H, H-5″), 2.54−
2.46 (m, 1H, CH), 1.18−1.10 (m, 4H, CH(CH2)2); 13C{1H} NMR
(75 MHz, DMSO-d6) δ 163.6 (C-6), 151.1 (C-2), 149.9 (C-4), 126.4
(C-8), 117.4 (C-5), 99.8 (C-7), 87.0 (C-1′), 85.2 (C-2′), 74.0 (C-4′),
70.7 (C-3′), 61.7 (C-5′), 14.0 (CH(CH2)2), 10.7 (CH(CH2)2);
HRMS (ESI-TOF) m/z: calcd for C14H17N3O4 ([M + H]+),
292.1291, found 292.1291.
1
a white solid (35 mg, 84%). H NMR (300 MHz, DMSO-d6) δ 8.83
(s, 1H, H-2), 8.18 (d, J = 8.8 Hz, 2H, Ph-H), 7.93 (d, J = 3.8 Hz, 1H,
H-8), 7.14 (d, J = 8.8 Hz, 2H, Ph-H), 7.01 (d, J = 3.8 Hz, 1H, H-7),
6.28 (d, J = 6.1 Hz, 1H, H-1′), 5.40 (d, JOH,2′ = 6.3 Hz, 1H, OH-2′),
6-Cyclopentyl-9-β-D-ribofuranosyl-7-deazapurine (11k). Fol-
lowing a similar procedure to that used for the synthesis of 11a,
compound 11k was obtained starting from 10k (80 mg, 0.126 mmol)
and 20 mL of 7 N NH3 in MeOH (2.38 g, 14.0 mmol) after column
chromatography on silica gel (CH2Cl2/MeOH = 10:1, v/v) as a white
5.21 (d, JOH,3′ = 4.7 Hz, 1H, OH-3′), 5.11 (dd, JOH,5′ = 5.9 Hz, JOH,5″
4.8 Hz, 1H, OH-5′), 4.47 (ddd, J2′,1′ = 6.3 Hz, J2′,3′ = 5.6 Hz, J2′,OH
=
=
6.3 Hz, 1H, H-2′), 4.14 (ddd, J3′,2′ = 5.6 Hz, J3′,4′ = 4.1 Hz, J3′,OH = 4.7
1
Hz, 1H, H-3′), 3.95 (ddd, J4′,3′ = 4.1 Hz, J4′,5′ = 3.9 Hz, J4′,5″ = 3.3 Hz,
semisolid (35 mg, 87%). H NMR (300 MHz, DMSO-d6) δ 8.70 (s,
1H, H-4′), 3.86 (s, 3H, CH3), 3.70−3.60 (ddd, J5′,4′ = 3.9 Hz, J5′,OH
=
1H, H-2), 8.07 (d, J = 8.0 Hz, 2H, Ph-H), 7.77 (d, J = 3.8 Hz, 1H, H-
8), 6.77 (d, J = 3.8 Hz, 1H, H-7), 6.19 (d, J = 6.1 Hz, 1H, H-1′), 5.36
(d, JOH,2′ = 6.3 Hz, 1H, OH-2′), 5.19 (d, JOH,3′ = 4.7 Hz, 1H, OH-3′),
5.13 (dd, JOH,5′ = 5.7 Hz, JOH,5″ = 4.3 Hz, 1H, OH-5′), 4.45 (ddd, J2′,1′
5.9 Hz, Jgem = 11.9 Hz, 1H, H-5′), 3.59−3.54 (ddd, J5″,4′ = 3.1 Hz,
J5″,OH = 5.0 Hz, Jgem = 11.9 Hz, 1H, H-5″), 3.48 (s, 3H, -OCH3);
13C{1H} NMR (75 MHz, DMSO-d6) δ 161.1 (C-6), 155.8 (C-Ph),
152.0 (C-4), 151.0 (C-2), 130.3 (C-Ph), 130.0 (C-Ph), 127.7 (C-8),
114.9 (C-Ph), 114.4 (C-5), 101.1 (C-7), 86.8 (C-1′), 85.3 (C-4′),
74.1 (C-2′), 70.7 (C-3′), 61.7 (C-5′), 55.4 (OCH3); HRMS (ESI-
TOF) m/z: calcd for C18H19N3O5 ([M + H]+), 358.1397, found
358.1391.
= 6.1 Hz, J2′,3′ = 4.9 Hz, J2′,OH = 6.3 Hz, 1H, H-2′), 4.13 (ddd, J3′,2′
=
4.9 Hz, J3′,4′ = 3.7 Hz, J3′,OH = 4.7 Hz, 1H, H-3′), 3.93 (ddd, J4′,3′ = 3.7
Hz, J4′,5′ = 4.5 Hz, J4′,5″ = 3.7 Hz, 1H, H-4′), 3.67−3.52 (ddd, J5′,4′
4.5 Hz, J5′,OH = 5.7 Hz, Jgem = 11.9 Hz, 1H, H-5′), 3.59−3.52 (ddd,
=
J5″,4′ = 3.7 Hz, J5″,OH = 4.3 Hz, Jgem = 11.9 Hz, 1H, H-5″), 2.09−1.62
(m, 8H); 13C{1H} NMR (75 MHz, DMSO-d6) δ 165.9 (C-6), 151.0
(C-2), 150.5 (C-4), 126.5 (C-8), 117.2 (C-5), 100.0 (C-7), 86.9 (C-
1′), 85.2 (C-2′), 74.0 (C-4′), 70.7 (C-3′), 61.7 (C-5′), 43.9
6-Phenyl-9-β-D-ribofuranosyl-7-deazapurine (11o). Follow-
ing a similar procedure to that used for the synthesis of 11a,
compound 11o was obtained starting from 10o (80 mg, 0.146 mmol)
M
J. Org. Chem. XXXX, XXX, XXX−XXX