Paper
Organic & Biomolecular Chemistry
δ = 170.9, 170.5, 138.2, 131.9, 131.1, 129.7, 125.6, 122.5, 73.2, 130.9, 128.7, 127.9, 125.5, 73.2, 70.0, 65.0, 62.9, 52.2, 26.7,
69.8, 65.1, 63.0, 21.2, 20.9 ppm.
21.1, 20.9 ppm. HRMS calcd for C18H20O6 + H+ (M + H)+:
4.1.5. p-Trifluoromethylphenyl 4,6-di-O-acetyl-2,3-dideoxy- 333.1338, found: 333.1337.
α-D-erythro-hex-2-enopyranoside (3e).35 Compound 3e was pre-
4.1.9. p-Carbomethoxyphenyl 4,6-di-O-acetyl-2,3-dideoxy-
pared according to the general procedure in 4.1 from 3,4,6-tri- α-D-erythro-hex-2-enopyranoside (3i).39 Compound 3i was pre-
O-acetyl-D-glucal, 1a (54 mg, 0.2 mmol), and bis(4-trifluoro- pared according to the general procedure in 4.1 from 3,4,6-tri-
methylphenyl)iodonium triflate, 2e (227 mg, 0.4 mmol), and O-acetyl-D-glucal, 1a (54 mg, 0.2 mmol), and bis(4-carbo-
obtained as
a colourless oil in 41% yield (29.2 mg, methoxyphenyl)iodonium triflate, 2i (219 mg, 0.4 mmol), and
1
0.082 mmol). H NMR (400 MHz, CDCl3) δ = 7.64 (d, J 8.0 Hz, obtained as a colourless oil in 49% yield (34 mg, 0.098 mmol).
2H), 7.54 (d, J 8.0 Hz, 2H), 6.19 (dq, J 1.6 Hz, 10.4 Hz, 1H), 6.02 1H NMR (400 MHz, CDCl3) δ = 8.02 (dd, J 1.6 Hz, 6.8 Hz, 2H),
(dt, J 2.4 Hz, 10.4 Hz, 1H), 5.36 (dt, J 1.2 Hz, 1H), 5.31–5.28 (m, 7.47 (d, J 8.4 Hz, 2H), 6.14 (dq, J 1.2 Hz, 10.4 Hz, 1H), 5.99 (dt,
1H), 4.28 (dd, J 6.0 Hz, 12.0 Hz, 1H), 4.12 (dd, J 3.2 Hz, 12.0 J 2.4 Hz, 10.4 Hz, 1H), 5.34 (q, J 2.4 Hz, 1H), 5.29–5.25 (m, 1H),
Hz, 1H), 3.83 (sext, 3.2 Hz, 1H), 2.09 (s, 3H), 2.08 (s, 3H) ppm. 4.25 (dd, J 6.4 Hz, 12.0 Hz, 1H), 4.10 (dd, J 2.8 Hz, 12.0 Hz,
13C NMR (100 MHz, CDCl3) δ = 170.8, 170.5, 143.3, 130.9, 1H), 3.90 (s, 3H), 3.81 (sext, J 3.2 Hz, 1H), 2.07 (s, 3H), 2.06 (s,
130.6 (q, 32.3 Hz), 128.1, 125.71, 125.66, 125.6, 124.2 (q, 270.4 3H) ppm. 13C NMR (100 MHz, CDCl3) δ = 170.8, 170.4, 166.8,
Hz), 73.0, 70.2, 65.0, 62.9, 21.1, 20.9 ppm. 19F NMR (376 MHz, 144.2, 131.0, 130.1, 129.9, 127.6, 125.5, 73.2, 70.0, 65.0, 62.9,
CDCl3) δ = −62.6 ppm.
4.1.6. p-Methylphenyl
52.2, 21.1, 20.8 ppm.
4.1.10. 4-Biphenyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-
4,6-di-O-acetyl-2,3-dideoxy-α-D-
erythro-hex-2-enopyranoside (3f).41 Compound 3f was pre- hex-2-enopyranoside (3j). Compound 3j was prepared accord-
pared according to the general procedure in 4.1 from 3,4,6-tri- ing to the general procedure in 4.1 from 3,4,6-tri-O-acetyl-D-
O-acetyl-D-glucal, 1a (54 mg, 0.2 mmol), and bis(4-tolyl)iodo- glucal, 1a (54 mg, 0.2 mmol), and bis(4-biphenyl)iodonium tri-
nium triflate, 2f (184 mg, 0.4 mmol), and obtained as a colour- flate, 2j (233 mg, 0.4 mmol), and obtained as a colourless oil
less oil in 75% yield (45.2 mg, 0.15 mmol). 1H NMR (400 MHz, in 55% yield (40 mg, 0.109 mmol). H NMR (400 MHz, CDCl3)
1
CDCl3) δ = 7.30 (d, J 8.0 Hz, 2H), 7.18 (d, J 8.0 Hz, 2H), δ = 7.62–7.34 (m, 9H), 6.23 (dq, J 1.6 Hz, 10.4 Hz, 1H), 6.02 (dt,
6.19–6.15 (m, 1H), 5.97 (dt, J 2.0 Hz, 10.4 Hz, 1H), 5.33–5.30 J 2.4 Hz, 10.4 Hz, 1H), 5.38 (q, J 2.4 Hz, 1H), 5.35–5.32 (m, 1H),
(m, 2H), 4.26 (dd, J 5.6 Hz, 12.0 Hz, 1H), 4.08 (dd, J 2.8 Hz, 4.30 (dd, J 6.0 Hz, 12.0 Hz, 1H), 4.13 (dd, J 3.2 Hz, 12.0 Hz,
12.0 Hz, 1H), 3.85–3.81 (m, 1H), 2.36 (s, 3H), 2.08 (s, 3H), 2.07 1H), 3.91–3.87 (m, 1H), 2.10 (s, 3H), 2.09 (s, 3H) ppm. 13C
(s, 3H) ppm. 13C NMR (100 MHz, CDCl3) δ = 170.9, 170.6, NMR (100 MHz, CDCl3) δ = 170.9, 170.6, 141.4, 140.8, 138.1,
138.2, 136.0, 131.8, 129.3, 128.1, 125.1, 73.8, 69.3, 65.3, 63.1, 131.7, 129.0, 128.5, 127.6, 127.4, 127.3, 125.3, 73.6, 69.7, 65.3,
21.3, 21.1, 20.9 ppm.
63.1, 21.2, 20.9 ppm. HRMS calcd for C22H22O5 + H+ (M + H)+:
4.1.7. p-tert-Butylphenyl
4,6-di-O-acetyl-2,3-dideoxy-α-D- 367.1544, found: 367.1545.
erythro-hex-2-enopyranoside (3g).40 Compound 3g was pre-
4.1.11. o-Methylphenyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-
pared according to the general procedure in 4.1 from 3,4,6- erythro-hex-2-enopyranoside (3k).35 Compound 3k was pre-
tri-O-acetyl-D-glucal, 1a (54 mg, 0.2 mmol), and bis(4-tert- pared according to the general procedure in 4.1 from 3,4,6-tri-
butylphenyl)iodonium triflate, 2g (217 mg, 0.4 mmol), and O-acetyl-D-glucal, 1a (54 mg, 0.2 mmol), and bis(2-tolyl)iodo-
obtained as
a colourless oil in 78% yield (54 mg, nium triflate, 2k (184 mg, 0.4 mmol), and obtained as a col-
0.156 mmol). 1H NMR (400 MHz, CDCl3) δ = 7.40 (dd, J 2.0 ourless oil in 60% yield (36.5 mg, 0.12 mmol). 1H NMR
Hz, 6.4 Hz, 2H), 7.34 (dd, J 2.0 Hz, 6.0 Hz, 2H), 6.20–6.17 (m, (400 MHz, CDCl3) δ = 7.31 (d, J 7.6 Hz, 1H), 7.27–7.16 (m, 3H),
1H), 5.98 (dt, J 2.4 Hz, 10.4 Hz, 1H), 5.33–5.30 (m, 2H), 4.28 6.13 (dq, J 1.2 Hz, 10.4 Hz, 1H), 6.04 (dt, J 2.4 Hz, 10.4 Hz, 1H),
(dd, J 6.0 Hz, 12.0 Hz, 1H), 4.10 (dd, J 3.2 Hz, 12.0 Hz, 1H), 5.49 (q, J 2.4 Hz, 1H), 5.32–5.29 (m, 2H), 4.25 (dd, J 6.0 Hz,
3.88–3.84 (m, 1H), 2.09 (s, 3H), 2.08 (s, 3H), 1.33 (s, 9H) ppm. 12.0 Hz, 1H), 4.03 (dd, J 3.2 Hz, 12.0 Hz, 1H), 3.79 (sext, J 3.2
13C NMR (100 MHz, CDCl3) δ = 170.9, 170.6, 151.4, 136.0, Hz, 1H), 2.46 (s, 3H), 2.09 (s, 3H), 2.03 (s, 3H) ppm. 13C NMR
131.9, 127.8, 125.6, 124.9, 73.7, 69.5, 65.3, 63.1, 34.7, 31.5, (100 MHz, CDCl3) δ = 170.9, 170.6, 138.3, 136.3, 132.1, 131.1,
21.2, 20.9 ppm.
128.7, 128.6, 125.6, 125.5, 71.4, 69.4, 65.4, 63.0, 21.2, 20.9,
4.1.8. p-Acetylphenyl
4,6-di-O-acetyl-2,3-dideoxy-α-D- 19.2 ppm.
erythro-hex-2-enopyranoside (3h).51 Compound 3h was pre-
4.1.12. m-Methylphenyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-
pared according to the general procedure in 4.1 from 3,4,6-tri- erythro-hex-2-enopyranoside (3l).39 Compound 3l was pre-
O-acetyl-D-glucal, 1a (54 mg, 0.2 mmol), and bis(4-acetylphe- pared according to the general procedure in 4.1 from 3,4,6-tri-
nyl)iodonium triflate, 2h (206 mg, 0.4 mmol), and obtained as O-acetyl-D-glucal, 1a (54 mg, 0.2 mmol), and bis(3-tolyl)iodo-
1
a colourless oil in 52% yield (34.3 mg, 0.103 mmol). H NMR nium triflate, 2l (184 mg, 0.4 mmol), and obtained as a colour-
(400 MHz, CDCl3) δ = 8.05 (d, J 8.4 Hz, 2H), 7.49 (d, J 8.0 Hz, less oil in 72% yield (43.8 mg, 0.12 mmol). 1H NMR (400 MHz,
2H), 6.20 (dq, J 1.6 Hz, 10.4 Hz, 1H), 6.01 (dt, J 2.8 Hz, 10.4 Hz, CDCl3) δ = 7.30–7.15 (m, 4H), 6.19 (dq, J 1.6 Hz, 10.4 Hz, 1H),
1H), 5.36 (q, J 2.0 Hz, 1H), 5.31–5.28 (m, 1H), 4.27 (dd, J 6.4 5.99 (dt, J 2.4 Hz, 10.0 Hz, 1H), 5.33–5.31 (m, 2H), 4.28 (dd, J
Hz, 12.0 Hz, 1H), 4.12 (dd, J 3.2 Hz, 12.0 Hz, 1H), 3.92 (s, 3H), 6.0 Hz, 12.0 Hz, 1H), 4.12 (dd, J 3.2 Hz, 12.0 Hz, 1H), 3.89–3.86
3.83 (sext, J 3.2 Hz, 1H), 2.09 (s, 3H), 2.08 (s, 3H) ppm. 13C (m, 1H), 2.39 (s, 3H), 2.10 (s, 3H), 2.09 (s, 3H) ppm. 13C NMR
NMR (100 MHz, CDCl3) δ = 197.7, 170.8, 170.4, 144.3, 137.0, (100 MHz, CDCl3) δ = 170.9, 170.6, 139.0, 138.4, 131.8, 129.1,
Org. Biomol. Chem.
This journal is © The Royal Society of Chemistry 2020