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X.-A. Zheng et al.
Paper
Synthesis
1H NMR (400 MHz, CDCl3): δ = 7.38–7.32 (m, 4 H), 7.32–7.25 (m, 1 H),
4.82–4.77 (m, 1 H), 3.65–3.57 (m, 2 H), 2.30–2.24 (m, 1 H), 0.95 (s, 9
H), 0.10 (s, 3 H), 0.06 (s, 3 H).
HRMS (ESI): m/z [M + H]+ calcd for C20H36NO4Si: 382.2408; found:
382.2404.
13C NMR (100 MHz, CDCl3): δ = 141.6, 128.4 (×2), 127.8, 126.4 (×2),
2′,3′-Di-O-(tert-butyldimethylsilyl)uridine (25′)
76.0, 69.0, 26.0 (×3), 18.3, –4.4, –4.8.
White solid; yield: 802 mg (85%); mp 226–228 °C.
MS (ESI): m/z = 253.2 [M + H]+.
1H NMR (400 MHz, DMSO-d6): δ = 11.35 (s, 1 H), 7.94 (d, J = 8.1 Hz, 1
H), 5.80 (d, J = 5.6 Hz, 1 H), 5.68 (d, J = 8.1 Hz, 1 H), 5.28–5.21 (m, 1 H),
4.28–4.21 (m, 1 H), 4.16–4.11 (m, 1 H), 3.88 (s, 1 H), 3.71–3.61 (m, 1
H), 3.60–3.51 (m, 1 H), 0.88 (s, 9 H), 0.82 (s, 9 H), 0.11–0.05 (m, 6 H),
0.04–0.01 (m, 6 H).
13C NMR (100 MHz, DMSO-d6): δ = 162.9, 150.7, 140.3, 102.0, 86.9,
85.5, 74.6, 71.8, 60.4, 25.7 (×3), 25.6 (×3), 17.7, 17.6, –4.7, –4.8, –4.9, –
5.1.
9H-Fluoren-9-ylmethyl 2-((tert-butyldimethylsilyl)oxy)-3-hy-
droxypropylcarbamate (20′)
Colorless oil; yield: 827 mg (97%).
1H NMR (400 MHz, CDCl3): δ = 7.77 (d, J = 7.5 Hz, 2 H), 7.62–7.56 (m, 2
H), 7.44–7.38 (m, 2 H), 7.35–7.28 (m, 2 H), 5.08 (t, J = 6.2 Hz, 1 H),
4.50–4.37 (m, 2 H), 4.22 (t, J = 6.8 Hz, 1 H), 3.88–3.79 (m, 1 H), 3.54–
3.38 (m, 3 H), 3.25–3.14 (m, 1 H), 2.76–2.65 (m, 1 H), 0.91 (s, 9 H),
0.09 (s, 6 H).
MS (ESI): m/z = 473.2 [M + H]+.
13C NMR (100 MHz, CDCl3): δ = 157.5, 144.0 (×2), 141.5 (×2), 127.9
(×2), 127.2 (×2), 125.2, 125.1, 120.2 (×2), 71.3, 67.0, 63.5, 47.4, 43.5,
26.0 (×3), 18.2, –4.5, –4.6.
3′-O-(tert-Butyldimethylsilyl)thymidine (26′)
White solid; yield: 627 mg (88%); mp 95–97 °C.
1H NMR (400 MHz, CDCl3): δ = 9.53 (br, 1 H), 7.41 (s, 1 H), 6.15 (t,
J = 6.7 Hz, 1 H), 4.51–4.44 (m, 1 H), 3.94–3.86 (m, 2 H), 3.77–3.69 (m,
1 H), 3.18 (br, 1 H), 2.35–2.27 (m, 1 H), 2.23–2.16 (m, 1 H), 1.87 (s, 3
H), 0.87 (s, 9 H), 0.06 (s, 6 H).
MS (ESI): m/z = 428.2 [M + H]+.
tert-Butyl 2-((tert-butyldimethylsilyl)oxy)-3-hydroxypropylcar-
bamate (21′)
13C NMR (100 MHz, CDCl3): δ = 164.3, 150.6, 137.2, 111.1, 87.8, 86.8,
Colorless oil; yield: 585 mg (96%).
71.7, 62.0, 40.7, 25.9 (×3), 18.1, 12.6, –4.6, –4.7.
1H NMR (400 MHz, CDCl3): δ = 4.85 (t, J = 6.1 Hz, 1 H), 3.83–3.76 (m,
1 H), 3.52–3.37 (m, 3 H), 3.13–3.01 (m, 2 H), 1.43 (s, 9 H), 0.88 (s, 9 H),
0.08–0.05 (m, 6 H).
MS (ESI): m/z = 357.2 [M + H]+.
(4-(((tert-Butyldimethylsilyl)oxy)methyl)phenyl)methanol (30′)
13C NMR (100 MHz, CDCl3): δ = 157.3, 80.0, 71.6, 63.4, 43.2, 28.5 (×3),
Colorless oil; yield: 453 mg (90%).
26.0 (×3), 18.2, –4.5, –4.6.
MS (ESI): m/z = 306.2 [M + H]+.
1H NMR (400 MHz, CDCl3): δ = 7.32 (s, 4 H), 4.74 (s, 2 H), 4.64 (d,
J = 5.1 Hz, 2 H), 2.13–2.07 (m, 1 H), 0.95 (s, 9 H), 0.11 (s, 6 H).
13C NMR (100 MHz, CDCl3): δ = 141.0, 139.7, 127.1 (×2), 126.4 (×2),
65.3, 64.9, 26.1 (×3), 18.6, –5.1 (×2).
3-((tert-Butyldimethylsilyl)oxy)-3-methylbutan-1-ol (22′)
Colorless oil; yield: 357 mg (82%).
1H NMR (400 MHz, CDCl3): δ = 3.83–3.76 (m, 2 H), 3.20–3.14 (m, 1 H),
1.69 (t, J = 5.8 Hz, 2 H), 1.28 (s, 6 H), 0.84 (s, 9 H), 0.13–0.09 (m, 6 H).
MS (ESI): m/z = 253.2 [M + H]+.
(4-(((Triisopropylsilyl)oxy)methyl)phenyl)methanol (31′)
13C NMR (100 MHz, CDCl3): δ = 75.5, 60.1, 45.8, 30.0 (×2), 26.0 (×3),
Colorless oil; yield: 558 mg (95%).
18.1, –1.8 (×2).
MS (ESI): m/z = 219.2 [M + H]+.
1H NMR (400 MHz, CDCl3): δ = 7.38–7.30 (m, 4 H), 4.84 (s, 2 H), 4.66
(d, J = 5.3 Hz, 2 H), 1.88 (t, J = 5.6 Hz, 1 H), 1.24–1.14 (m, 3 H), 1.13–
1.07 (m, 18 H).
13C NMR (100 MHz, CDCl3): δ = 141.4, 139.5, 127.1 (×2), 126.1 (×2),
(2-((tert-Butyldimethylsilyl)oxy)phenyl)methanol (23′)
Colorless oil; yield: 447 mg (94%).
65.4, 65.0, 18.2 (×6), 12.2 (×3).
1H NMR (400 MHz, CDCl3): δ = 7.35–7.30 (m, 1 H), 7.22–7.15 (m, 1 H),
7.00–6.94 (m, 1 H), 6.83 (d, J = 6.4 Hz, 1 H), 4.68 (d, J = 6.2 Hz, 2 H),
2.36 (t, J = 6.3 Hz, 1 H), 1.04 (s, 9 H), 0.27 (s, 6 H).
MS (ESI): m/z = 295.2 [M + H]+.
(4-(((tert-Butyldiphenylsilyl)oxy)methyl)phenyl)methanol (32′)
13C NMR (100 MHz, CDCl3): δ = 153.5, 131.6, 128.9, 128.7, 121.5,
Colorless oil; yield: 705 mg (94%).
118.5, 61.9, 25.9 (×3), 18.3, –4.0 (×2).
MS (ESI): m/z = 239.1 [M + H]+.
1H NMR (400 MHz, CDCl3): δ = 7.80–7.74 (m, 4 H), 7.51–7.35 (m, 10
H), 4.83 (s, 2 H), 4.70 (s, 2 H), 2.09 (s, 1 H), 1.16 (s, 9 H).
13C NMR (100 MHz, CDCl3): δ = 140.7, 139.7, 135.7 (×5), 133.6, 129.9
(×2), 127.9 (×4), 127.1 (×2), 126.4 (×2), 65.5, 65.3, 27.0 (×3), 19.5.
MS (ESI): m/z = 377.2 [M + H]+.
tert-Butyl 2-(4-((tert-butyldimethylsilyl)oxy)phenyl)-2-hy-
droxyethyl(methyl)carbamate (24′)
White solid; yield: 632 mg (83%); mp 41–42 °C.
IR (KBr): 3253, 2912, 1725, 1675, 1394, 1215, 1030 cm–1
.
4-((tert-Butyldimethylsilyl)oxy)-4-methylpentan-2-ol (34′)
1H NMR (400 MHz, CDCl3): δ = 7.19 (d, J = 8.2 Hz, 2 H), 6.80 (d, J = 8.2
Hz, 2 H), 4.86–4.82 (m, 1 H), 4.16–4.13 (m, 1 H), 3.51–3.30 (m, 2 H),
2.80 (s, 3 H), 1.45 (s, 9 H), 0.97 (s, 9 H), 0.17 (s, 6 H).
Colorless oil; yield: 394 mg (85%).
1H NMR (400 MHz, CDCl3): δ = 4.31 (s, 1 H), 4.21–4.12 (m, 1 H), 1.71–
1.65 (m, 1 H), 1.42–1.37 (m, 1 H), 1.34 (s, 3 H), 1.30 (s, 3 H), 1.14 (d,
J = 6.2 Hz, 3 H), 0.87 (s, 9 H), 0.15 (s, 6 H).
13C NMR (100 MHz, CDCl3): δ = 158.0, 155.3, 135.2, 127.1 (×2), 120.1
(×2), 80.3, 73.4, 57.6, 36.5, 28.5 (×3), 25.8 (×3), 18.3, –4.3 (×2).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–I