Beilstein J. Org. Chem. 2012, 8, 522–527.
diluted with EtOAc (20 mL), washed with water (2 × 30 mL) (0.05 g, 0.07 mmol) in DMF/THF/Et3N 5:3:2 (1 mL) was
and brine (2 × 10 mL), dried (Na2SO4) and concentrated in admixed with Pd(PPh3)2Cl2 (0.01 g, 20 mol %) under a N2
vacuo. The crude reaction mixture was purified (hexane/EtOAc atmosphere, and was followed by the addition of CuI (0.012 g,
92:8) to afford 7 (0.042 g, 80%), as an oil. Rf 0.60 (hexane/ 10 mol %) and 1-octyne (0.023 mL, 0.14 mmol), in a
EtOAc 9:1); [α]D −58.8 (c 0.5, CHCl3); 1H NMR (400 MHz, sealed tube. The reaction mixture was stirred at 98 °C for 72 h,
CDCl3) δ 7.44 (d, J = 7.6 Hz, 2H, aromatic), 7.33–7.21 (m, cooled, filtered, diluted with EtOAc (20 mL), washed
21H, aromatic), 7.18 (d, J = 4.8 Hz, 2H, aromatic), 5.30 (app. s, with water (2 × 30 mL) and brine (2 × 10 mL), dried (Na2SO4)
1H, CHH=CPh), 5.14 (app. s, 1H, CHH=CPh), 4.98 (s, 1H, and concentrated in vacuo. The crude reaction mixture
H-1), 4.58 (d, J = 12.4 Hz, 2H, PhCH2), 4.44 (d, J = 12.0 Hz, was purified (hexane/EtOAc 9:1) to afford 12 (0.035 g, 68%),
2H, PhCH2), 4.31 (d, J = 10.8 Hz, 2H, PhCH2), 4.22 (d, J = as an oil. Rf 0.30 (hexane/EtOAc 9:1); [α]D +4.56 (c 0.1,
11.6 Hz, 1H, PhCH2), 4.08–4.03 (band, 3H, H-4, H-6 and CHCl3); 1H NMR (400 MHz, CDCl3) δ 7.36–7.21 (m, 18H,
PhCH2), 3.88 (d, J = 14.4 Hz, 1H, -CHH C(Ph)=CH2), 3.61 (dd, aromatic), 7.07–7.05 (m, 2H, aromatic), 5.25 (s, 1H, H-1), 5.08
J = 9.2, 1.6 Hz, 1H, H-5), 3.55 (dd, J = 10.4, 6.4 Hz, 1H, H-7a), (d, J = 11.6 Hz, 1H, PhCH2), 4.80 (d, J = 11.6 Hz, 1H, PhCH2),
3.49 (dd, J = 8.8, 2.0 Hz, 1H, H-7b), 3.36 (s, 3H, OMe), 3.08 4.72 (d, J = 12.4 Hz, 1H, PhCH2), 4.60 (d, J = 12.4 Hz, 1H,
(d, J = 14.4 Hz, 1H, -CHH C(Ph)=CH2); 13C NMR (100 MHz, PhCH2), 4.45 (d, J = 12.4 Hz, 2H, PhCH2), 4.32 (d, J =
CDCl3) δ 150.9 (C-3), 146.3 (CH2-C(Ph)=CH2), 141.0–137.3 11.6 Hz, 1H, PhCH2), 4.17 (d, J = 11.6 Hz, 1H, PhCH2),
(aromatic), 128.3–126.6 (aromatic), 126.5 (C-2), 114.1 (C-10), 4.14–4.10 (band, 2H, H-4 and H-6), 3.68 (dd, J = 8.8, 2.0 Hz,
101.0 (C-1), 80.8 (C-5), 76.3 (C-4), 72.9 (PhCH2), 72.0 1H, H-5), 3.60 (dd, J = 6.0, 3.0 Hz, 1H, H-7a), 3.52–3.49 (br,
(PhCH2), 71.7 (PhCH2), 71.3 (PhCH2), 71.2 (C-7), 70.0 (C-6), 1H, H-7b), 3.48 (s, 3H, OMe), 2.37 (t, J = 7.2 Hz, 2H,
55.7 (OMe) 33.2 (-CH2-C(Ph)=CH2); HRMS–ESI (m/z): [M + -C≡CCH2-), 1.55–1.51 (m, 1H, -C≡CCH2CH2-), 1.42–1.35 (m,
Na]+ calcd for 705.3192; found, 705.3193.
1H, -C≡CCH2CH2-), 1.30–1.18 (m, 6H, -C≡C(CH2)2(CH2)3-),
0.86 (t, J = 6.8 Hz, 3H, -C≡C(CH2)5CH3); 13C NMR
Methyl 2-deoxy-2-C-(p-methoxyphenyl)-3,4,5,7-tetra-O- (100 MHz, CDCl3) δ 160.9 (C-3), 138.4–137.5 (aromatic),
benzyl-α-D-arabino-hept-2-enoseptanoside (9): A solution of 128.4–127.4 (aromatic), 109.9 (C-2), 100.8 (C-1), 97.4
2 [21] (0.05 g, 0.07 mmol) in 1,4-dioxane (1 mL) was admixed (-C≡CCH2CH2-), 80.4 (C-5), 78.6 (C-4), 75.7 (-C≡CCH2CH2-),
with Pd(OAc)2 (1 mg, 10 mol %) under a N2 atmosphere, and 73.3 (PhCH2), 72.8 (PhCH2), 71.8 (PhCH2), 71.2 (PhCH2),
was followed by the addition of Cs2CO3 (0.03 g, 0.11 mmol) 71.1 (C-6), 70.8 (C-7), 55.9 (OMe), 31.3 (-C≡C(CH2)3CH2-),
and 4-methoxyphenylboronic acid (0.012 g, 0.07 mmol), in a 28.6 (-C≡C(CH2)4CH2-), 28.5 (-C≡CCH2CH2-), 22.5
sealed tube. The reaction mixture was stirred at 98 °C for 72 h, (-C≡C(CH2)2CH2-), 20.0 (-C≡CCH2(CH2)4CH3), 14.3
cooled, filtered, diluted with EtOAc (20 mL), washed (-C≡C(CH2)5CH3); HRMS–ESI (m/z): [M + Na]+ calcd for
with water (2 × 30 mL) and brine (2 × 10 mL), dried (Na2SO4) 697.3505; found, 697.3507.
and concentrated in vacuo. The crude reaction mixture was
purified (hexane/EtOAc 8:2) to afford 9 (0.033 g, 64%), as an Methyl 2-deoxy-2-C-(2-(tert-butoxycarbonyl)ethyl)-α-D-
oil. Rf 0.60 (hexane/EtOAc 8:2); [α]D −9.8 (c 0.1, CHCl3); manno-sept-3-uloside (13): A mixture of 4 (0.038 g,
1H NMR (400 MHz, CDCl3) δ 7.38–7.11 (m, 20H, aromatic), 0.054 mmol) and Pd/C (10%, 0.030 g) in MeOH (10 mL) was
6.88 (d, J = 7.6 Hz, 2H, aromatic), 6.83 (d, J = 8.8 Hz, 2H, stirred under a positive pressure of H2 for 24 h at rt, filtered
aromatic), 5.37 (s, 1H, H-1), 4.81 (d, J = 12.4 Hz, 1H, PhCH2), through a celite pad, and washed with MeOH (2 × 15 mL), and
4.64–4.49 (m, 3H, PhCH2), 4.40 (d, J = 11.6 Hz, 2H, PhCH2), the solvents were removed in vacuo to afford 13 (0.017 g,
4.32–4.29 (br, 1H, H-6), 4.28 (app. d, J = 11.2 Hz, 1H, H-4), 94%), as an oil. Rf 0.3 (MeOH/CHCl3 1:1); [α]D +63.12 (c 0.5,
4.23 (s, 2H, PhCH2), 3.80 (s, 3H, OMe), 3.77–3.74 (br, 1H, MeOH); 1H NMR (400 MHz, CD3OD) δ 4.37 (d, J = 8.0 Hz,
H-5), 3.66 (dd, J = 10.6, 6.4 Hz, 1H, H-7a), 3.58 (dd, J = 10.6, 1H, H-1), 4.28 (app. d, J = 7.6 Hz, 1H, H-4), 4.08 (m, 1H, H-6),
2.4 Hz, 1H, H-7b), 3.33 (s, 3H, OMe); 13C NMR (100 MHz, 3.85 (dd, J = 13.6, 2.4 Hz, 1H, H-7a), 3.73 (dd, J = 13.6, 4.8
CDCl3) δ 158.4 (aromatic), 152.3 (C-3), 138.4–137.3 Hz, 1H, H-7b), 3.46 (s, 3H, OMe), 3.35 (br, 1H, H-5),
(aromatic), 130.9 (aromatic), 129.0 (C-2), 128.4–127.4 3.22–3.17 (m, 1H, H-2), 2.21 (t, J = 7.4 Hz, 2H, -CH2-
(aromatic), 113.1 (aromatic), 102.2 (C-1), 80.7 (C-5), 78.3 CH2CO2t-Bu), 2.10–2.01 (m, 1H, -CHHCH2CO2t-Bu),
(C-4), 73.0 (PhCH2), 72.6 (PhCH2), 72.0 (PhCH2), 71.2 (C-6), 1.83–1.75 (m, 1H, -CHHCH2CO2t-Bu), 1.49 (s, 9H, t-Bu);
71.1 (C-7), 55.9 (OMe), 55.2 (-C6H4OMe); HRMS–ESI (m/z): 13C NMR (100 MHz, CD3OD) δ 208.4 (C-3), 175.3 (C=O),
[M + Na]+ calcd for 695.2985; found, 695.2983.
103.4 (C-1), 84.5 (C-4), 83.1 (C-t-Bu), 73.2 (C-5), 71.0 (C-6),
62.7 (C-7), 56.6 (OMe), 52.2 (C-2), 33.9 (-CH2CH2CO2t-Bu),
Methyl 2-deoxy-2-C-(octyn-1-yl)-3,4,5,7-tetra-O-benzyl-α-D- 28.2 (t-Bu), 23.3 (-CH2CH2CO2t-Bu); HRMS–ESI (m/z): [M +
arabino-hept-2-enoseptanoside (12): A solution of 2 [21] Na]+ calcd for 357.1525; found, 357.1526.
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