Paper
Organic & Biomolecular Chemistry
(–CO-β), 165.7 (C-4), 152.2 (C-2), 152.1, 152.0 (phenyl C), 141.9, (C-α-asp), 40.4–40.2 (C-β-asp), 30.2–29.9 (–OCH2(CH2)2-
141.8 (C-6), 130.9 (phenyl C), 126.3 (phenyl C), 121.3 (phenyl CH2CH3), 24.2 (–O(CH2)3CH2CH3), 21.1, 21.0 (CH3-2′),
C), 102.9, 102.8 (C-5), 93.5, 93.3 (C-1′), 81.5, 81.4 (C-4′), 79.6, 15.2 ppm (–O(CH2)4CH3); 31P NMR (202 MHz, MeOD): δ = 3.74
79.5 (C-2′), 73.9, 73.7 (C-3′), 70.7, 69.8, 69.7 –CH(CH3)2), 66.4 and 3.57 ppm; HRMS (ESI+) calcd for C30H45N3O12P [M + H]+
(d, 2JCP = 4.52 Hz, C-5′), 65.9 (d, 2JCP = 4.73 Hz, C-5′), 52.8, 52.7 670.2735, found 670.2736.
(–C-α-asp), 39.9–39.7 (–H-β-asp), 22.0–21.9 ppm (–CH(CH3)2),
2′-C-Methyl-2′,3′-O-isopropyliden-uridine-5′-[phenylbis-(isoamyl-
20.2 (2′-CH3); 31P NMR (202 MHz, MeOD): δ = 3.82 and L-aspartyl)]phosphate (protected 2g). Yield: 87%; Rf = 0.65
3.59 ppm; HRMS (ESI−) calcd for C26H35N3O12P [M − H]− (CH2Cl2–MeOH, 9.5 : 0.5); 31P NMR (121 MHz, CDCl3): δ = 3.24
612.1964, found 612.1964.
2′-C-Methyl-2′,3′-O-isopropyliden-uridine-5′-[phenylbis(n-butyl- 710.3048, found 710.3050.
and 2.78 ppm; HRMS (ESI+) calcd for C33H49N3O12P [M + H]+
L-aspartyl)]phosphate (protected 2e). Yield: 86%; Rf = 0.45
2′-C-Methyl-uridine-5′-[phenylbis(isoamyl-L-aspartyl)]phos-
1
(CH2Cl2–MeOH, 9.5 : 0.5); 31P NMR (121 MHz, CDCl3): δ = 3.24 phate (2g). Yield: 86%; Rf = 0.25 (EtOAc–hexane, 9.0 : 1.0); H
and 2.77; HRMS (ESI−) calcd for C31H43N3O12P [M − H]− NMR (600 MHz, MeOD): δ = 7.68–7.66 (2 d, 1H, H-6), 7.38–7.18
680.2590, found 680.2593.
2′-C-Methyl-uridine-5′-[phenylbis(n-butyl-L-aspartyl)]phosphate 5.65–5.61 (2 d, 1H, H-5), 4.62–4.38 (m, 2H, H-5′ & H-5″),
(2e). Yield: 80%; Rf = 0.2 (CH2Cl2–MeOH, 9.5 : 0.5); 1H NMR 4.31–4.25 (m, 1H, H-α-Asp), 4.19–4.02 (m, 5H, H-4′
(a series of multiplets, 5H, OPh), 5.98, 5.97 (2 s, 1H, H-1′),
&
(500 MHz, MeOD): δ = 7.68–7.66 (2 d, 1H, H-6), 7.38–7.18 (a –OCH2CH2CH(CH3)2), 3.84–3.80 (d, 1H, H-3′), 2.83–2.69 (m,
series of multiplets, 5H, OPh), 5.98, 5.97 (2 s, 1H, H-1′), 2H, H-β-Asp), 1.68–1.62 (m, 2H, –OCH2CH2CH(CH3)2),
5.65–5.63 (2 d, 1H, H-5), 4.62–4.37 (m, 2H, H-5′ & H-5″), 1.52–1.46 (m, 4H, –OCH2CH2CH(CH3)2), 1.16, 1.13 (2 s, 3H,
4.32–4.26 (m, 1H, H-α-Asp), 4.16–3.98 (m, 5H, H-4′
–OCH2(CH2)2CH3), 3.84–3.80 (2 d, 1H, H-3′), 2.84–2.69 (m, 2H, NMR (150 MHz, MeOD): δ = 173.9 (d, JCP = 4.84 Hz, –CO-α),
H-β-Asp), 1.62–1.53 (m, 4H, –OCH2CH2CH2CH3), 1.40–1.31 (m, 173.7 (d, JCP = 5.68 Hz, –CO-α), 172.7, 172.6 (–CO-β), 166.8,
&
–CH3-2′), 0.91–0.90 ppm (m, 12H, –OCH2CH2CH(CH3)2); 13C
3
3
4H, –O(CH2)2CH2CH3), 1.16 and 1.13 (2 s, 3H, –CH3-2′), 166.6 (C-4), 153.1 (C-2), 153.0, 152.9 (phenyl C), 142.8, 142.7
0.93–0.90 ppm (m, 6H, –O(CH2)3CH3); 13C NMR (125 MHz, (C-6), 131.8, 131.6 (phenyl C), 127.1 (phenyl C), 122.2, 122.1
3
3
MeOD): δ = 174.0 (d, JCP = 4.89 Hz, –CO-α), 173.7 (d, JCP
=
(phenyl C), 103.7 (C-5), 94.3, 94.2 (C-1′), 82.4, 82.3 (C-4′), 80.5,
2
5.91 Hz, –CO-α), 172.7 (–CO-β), 166.7 (C-4), 153.1 (C-2), 153.0, 80.4 (C-2′), 74.8, 74.5 (C-3′), 67.2 (d, JCP = 4.63 Hz, C-5′), 66.8
152.9 (phenyl C), 142.8, 142.7 (C-6), 131.8 (phenyl C), 127.1 (d, JCP = 4.32 Hz, C-5′), 66.2, 65.6, 65.5 (–OCH2CH2CH(CH3)2),
2
(phenyl C), 122.2, 122.1 (phenyl C), 103.7 (C-5), 94.3, 94.2 53.6, 53.5 (C-α-asp), 40.4–40.2 (C-β-asp), 39.2, 39.1
(C-1′), 82.4, 82.3 (C-4′), 80.5, 80.4 (C-2′), 74.8, 74.6 (C-3′), (–OCH2CH2CH(CH3)2), 27.0, 26.9 (–OCH2CH2CH(CH3)2), 23.7,
67.5–66.7 (C-5′ & –OCH2(CH2)2CH3), 53.6, 53.5 (C-α-asp), 23.6 (–OCH2CH2CH(CH3)2), 21.1 ppm (CH3-2′); 31P NMR
40.4–40.2 (C-β-asp), 32.5 (–OCH2CH2CH2CH3), 21.1–20.9 (CH3- (202 MHz, MeOD): δ = 3.72 and 3.56 ppm; HRMS (ESI+) calcd
2′ & –O(CH2)2CH2CH3), 14.9 ppm (–O(CH2)3CH3); 31P NMR for C30H45N3O12P [M − H]− 670.2735, found 670.2741.
(202 MHz, MeOD): δ = 3.73 and 3.57 ppm; HRMS (ESI+) calcd
2′-C-Methyl-2′,3′-O-isopropyliden-uridine-5′-[phenylbis(methoxy-
iminodiacetyl)]phosphate (protected 2h). Yield: 80%, Rf = 0.5
for C28H39N3O12P [M + H]+ 642.2422, found 642.2429.
2′-C-Methyl-2′,3′-O-isopropyliden-uridine-5′-[phenylbis(amyl- (CH2Cl2–MeOH, 9.5 : 0.5); 1H NMR (300 MHz, CDCl3): δ =
L-aspartyl)]phosphate (protected 2f). Yield: 72%; Rf = 0.35 7.57–7.52 (2 d, 1H, H-6), 7.37–7.15 (a series of multiplets, 5H,
(EtOAc–hexane, 9.0 : 1.0); 31P NMR (121 MHz, CDCl3): δ = 3.25 OPh), 6.10, 6.09 (2 s, 1H, H-1′), 5.72–5.59 (2 d, 1H, H-5),
and 2.77 ppm; HRMS (ESI+) calcd for C33H47N3O12P [M + H]+ 4.51–4.34 (m, 4H), 4.12–3.93 (m, 4H), 3.69 (m, 6H, –OCH3),
710.3048, found 710.3059.
1.60, 1.59 (s, 3H, –CH3), 1.40, 1.39 (s, 3H, –CH3), 1.21,
2′-C-Methyl-uridine-5′-[phenylbis(amyl-L-aspartyl)]phosphate 1.18 ppm (2 s, 3H, –CH3-2′); 31P NMR (121 MHz, CDCl3): δ =
(2f). Yield: 60%; Rf = 0.4 (CH2Cl2–MeOH, 9.5 : 0.5); 1H NMR 4.28 and 4.05 ppm; HRMS (ESI+) calcd for C25H33N3O12P
(600 MHz, MeOD): δ = 7.68–7.66 (2 d, 1H, H-6), 7.38–7.18 (a [M + H]+ 598.1796, found 598.1799.
series of multiplets, 5H, OPh), 5.98, 5.97 (2 s, 1H, H-1′),
5.65–5.61 (2 d, 1H, H-5), 4.62–4.38 (m, 2H, H-5′ & H-5″), phate (2h). Yield: 50%, Rf = 0.47 (CH2Cl2–MeOH, 9.3 : 0.7); H
4.31–4.26 (m, 1H, H-α-Asp), 4.15–3.99 (m, 5H, H-4′ NMR (500 MHz, MeOD): δ = 7.69–7.58 (2 d, 1H, H-6), 7.39–7.19
2′-C-Methyl-uridine-5′-[phenylbis(methoxyiminodiacetyl)]phos-
1
&
–OCH2(CH2)3CH3), 3.83–3.80 (d, 1H, H-3′), 2.84–2.70 (m, 2H, (a series of multiplets, 5H, OPh), 5.99, 5.98 (2 s, 1H, H-1′),
H-β-Asp), 1.61–1.57 (m, 4H, –OCH2CH2(CH2)2CH3), 1.35–1.27 5.67–5.61 (2 d, 1H, H-5), 4.71–4.36 (m, 2H, H-5′ & H-5″),
(m, 8H, –O(CH2)2(CH2)2CH3), 1.16 and 1.13 (2 s, 3H, –CH3-2′), 4.13–3.95 (m, 5H, H-4′, –CH2-IDA), 3.83–3.73 (2 d, 1H, H-3′),
0.91–0.88 ppm (m, 6H, –O(CH2)4CH3); 13C NMR (150 MHz, 3.68 (s, 6H, –OCH3), 1.16 and 1.12 ppm (2 s, 3H, –CH3-2′); 13C
3
3
MeOD): δ = 173.9 (d, JCP = 4.70 Hz, –CO-α), 173.7 (d, JCP
=
NMR (125 MHz, MeOD): δ = 171.8 (–CO), 165.9, 165.8 (C-4),
5.75 Hz, –CO-α), 172.7 (–CO-β), 166.6 (C-4), 153.1 (C-2), 153.0, 152.3 (C-2), 152.0–151.9 (phenyl C), 142.1, 141.8 (C-6), 131.0,
152.9 (phenyl C), 142.8, 142.7 (C-6), 131.8, 131.7 (phenyl C), 130.9 (phenyl C), 126.4 (phenyl C), 121.2–121.1 (phenyl C),
127.1 (phenyl C), 122.2 (phenyl C), 103.7 (C-5), 94.2 (C-1′), 103.0, 102.9 (C-5), 93.5, 93.2 (C-1′), 81.4–81.2 (C-4′), 79.6, 79.5
2
82.4, 82.3 (C-4′), 80.5, 80.4 (C-2′), 74.8, 74.5 (C-3′), 67.7 (C-2′), 74.1, 73.7 (C-3′), 66.8 (d, JCP = 4.90 Hz, C-5′), 65.9 (d,
2
(–OCH2(CH2)3CH3), 67.2 (d, JCP = 4.35 Hz, C-5′), 67.1, 67.0 2JCP = 4.35 Hz, C-5′), 52.6 (–OCH3), 49.1 (–CH2-IDA), 20.3,
2
(–OCH2(CH2)3CH3), 66.8 (d, JCP = 3.87 Hz, C-5′), 53.6, 53.5 20.2 ppm (2′-CH3); 31P NMR (202 MHz, MeOD): δ = 4.36 and
Org. Biomol. Chem.
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