Vol. 64, No. 7 (2016)
Chem. Pharm. Bull.
911
J=7.0Hz, 2H), 7.49 (t, J=7.8Hz, 2H), 7.48 (t, J=7.8Hz, 2H), 1714, 1272cm−1. MS (FAB) m/z (rel intensity) 661 (M+Na+,
6.59 (s, 1H), 5.67 (d, J=7.2Hz, 1H), 5.01 (d, J=8.0Hz, 1H), 10), 639 (M+H+, 1), 154 (100). HR-MS (FAB) m/z Calcd for
4.93 (t, J=7.8Hz, 1H), 4.60–4.52 (m, 1H), 4.33 (d, J=8.4Hz, C34H38O12Na (M+Na)+ 661.2261. Found 661.2264.
1H), 4.17 (d, J=8.4Hz, 1H), 3.96 (d, J=6.8Hz, 1H), 2.71–2.55
7-O-Trichloroacetyl-10-deacetylbaccatin III
(m, 2H), 2.39–2.26 (m, 5H), 2.16 (brs, 1H), 2.11 (s, 3H),
Colorless needle. mp 218°C (dec.). [α]D20 −27 (c=0.50,
1.95–1.84 (m, 1H), 1.693 (s, 3H), 1.690 (brs, 1H), 1.23 (s, CHCl3). 1H-NMR (400MHz, CDCl3) δ: 8.10 (dd, J=8.4,
3H), 1.19 (s, 3H). 13C-NMR (100MHz, CDCl3) δ: 204.0, 170.7, 2.4Hz, 2H), 7.62 (t, J=7.2Hz, 1H), 7.49 (t, J=7.6Hz, 2H),
167.1, 166.4, 146.6, 133.7, 133.6, 131.8, 130.1, 130.0, 129.25, 5.65 (d, J=6.8Hz, 1H), 5.56 (dd, J=10.4, 7.2Hz, 1H), 5.32
129.17, 128.6, 128.5, 84.5, 80.8, 79.1, 76.6, 76.4, 74.9, 72.4, (s, 1H), 4.99 (d, J=8.4Hz, 1H), 4.88 (t, J=7.6Hz, 1H), 4.35
68.0, 58.7, 46.2, 42.7, 38.5, 35.7, 27.2, 22.6, 21.2, 15.7, 9.4. (d, J=8.8Hz, 1H), 4.19 (d, J=8.0Hz, 1H), 4.10 (d, J=6.8Hz,
IR (neat) 3483, 2942, 1717, 1451, 1270cm−1. MS (FAB) m/z 1H), 3.99 (brs, 1H), 2.78–2.65 (m, 1H), 2.34–2.23 (m, 5H),
(rel intensity) 671 (M+Na+, 2), 154 (100). HR-MS (FAB) m/z 2.12 (s, 3H), 2.10–2.00 (m, 2H), 1.92 (s, 3H), 1.08 (s, 3H), 1.07
Calcd for C36H40O11Na (M+Na)+ 671.2468. Found 671.2462.
10-O-Cinnamoyl-10-deacetylbaccatin III
(s, 3H). 13C-NMR (100MHz, CDCl3) δ: 209.9, 170.9, 166.9,
161.0, 142.8, 134.3, 133.8, 130.1, 129.1, 128.7, 83.3, 80.1, 78.7,
Colorless microcrystal. mp 152–157°C. [α]D20 −79 (c=0.70, 77.9, 76.4, 74.9, 74.3, 67.8, 56.1, 46.7, 42.5, 38.5, 32.5, 26.6,
CHCl3). 1H-NMR (400MHz, CDCl3) δ: 8.11 (dd, J=7.2, 22.5, 19.4, 15.0, 10.8. IR (neat) 3466, 2949, 1767, 1715, 1452,
1.2Hz, 2H), 7.78 (d, J=16.4Hz, 1H), 7.65–7.53 (m, 3H), 7.49 1244cm−1. MS (FAB) m/z (rel intensity) 689 (M+H+, 2), 185
(t, J=7.8Hz, 2H), 7.44–7.37 (m, 3H), 6.59 (d, J=15.6Hz, 1H), (60), 105 (100). HR-MS (FAB) m/z Calcd for C31H36O11Cl3
6.47 (s, 1H), 5.65 (d, J=7.2Hz, 1H), 5.01 (d, J=7.6Hz, 1H), (M+H)+ 689.1323. Found 689.1310.
4.92 (brt, 1H), 4.56–4.50 (m, 1H), 4.32 (d, J=8.4Hz, 1H), 4.17
(d, J=8.0Hz, 1H), 3.92 (d, J=7.2Hz, 1H), 2.73 (d, J=4.0Hz,
10-Deacetylbaccatin III Dimer 12
To a solution of pivaloyl chloride (28µL, 230µmol, 2.5eq)
1H), 2.65–2.53 (m, 1H), 2.34–2.25 (m, 5H), 2.18 (brd, 1H), was added undecanedioic acid (10mg, 46µmol, 0.5eq) and
2.09 (s, 3H), 1.94–1.83 (m, 1H), 1.69 (s, 3H), 1.67 (s, 1H), 1.17 DIPEA (47µL, 347µmol, 3.8eq) in CH2Cl2 (1.0mL) dropwise
(s, 3H), 1.16 (s, 3H). 13C-NMR (100MHz, CDCl3) δ: 204.2, at room temperature, and the mixture was stirred at room
170.7, 167.1, 166.9, 146.7, 146.6, 134.1, 133.7, 131.9, 130.7, temperature for 2h. The resulting mixture was concentrated
130.1, 129.3, 128.9, 128.6, 128.3, 116.9, 84.5, 80.8, 79.1, 76.4, in vacuo and diluted with CHCl3 (1.0mL). The resulting mix-
76.2, 74.9, 72.4, 68.0, 58.7, 46.1, 42.7, 38.5, 35.6, 27.1, 22.6, ture was added to a precooled solution of 1 (50mg, 92µmol,
21.1, 15.7, 9.4. IR (neat) 3523, 2942, 1715, 1633, 1452cm−1. 1.0eq), 6 (7.6mg, 9.2µmol, 10mol%) and collidine (37µg,
MS (FAB) m/z (rel intensity) 697 (M+Na+, 2), 676 (M+H, 1), 280µmol, 3.0eq) in CHCl3 (8.0mL, total 9.0mL) at −20°C
154 (100). HR-MS (FAB) m/z Calcd for C38H42O11Na (M+Na)+ (final concentration of 1: 0.01M). After stirred at −20°C
697.2625. Found 697.2632.
for 30h, the reaction mixture was quenched with methanol
(5.0mL) and stired at room temperature for 1h. The mixture
10-O-2-Thiophenyl-10-deacetylbaccatin III
Colorless powder. mp 175–179°C. [α]D20 −60 (c=0.55, was diluted with AcOEt and washed with 1M HCl, saturated
1
THF). H-NMR (400MHz, CDCl3) δ: 8.11 (dd, J=7.6, 1.2Hz, aq. NaHCO3, and brine, dried over Na2SO4, filtered and con-
2H), 7.89 (dd, J=7.6, 1.2Hz, 1H), 7.65–7.57 (m, 2H), 7.49 centrated in vacuo. The residue was purified by preparative
(t, J=7.8Hz, 2H), 7.15 (dd, J=5.0, 3.8Hz, 1H), 6.53 (s, 1H), TLC (AcOEt–hexane=80:20) to give a 10-deacetylbaccatin
5.66 (d, J=6.8Hz, 1H), 5.00 (d, J=8.0Hz, 1H), 4.92 (brt, III dimer 12 as colorless amorphous (23mg, 40% yield as a
1
1H), 4.55–4.48 (m, 1H), 4.32 (d, J=8.4Hz, 1H), 4.16 (d, single isomer). [α]D20 −75 (c=1.0, THF). H-NMR (400MHz,
J=8.4Hz, 1H), 3.94 (d, J=6.8Hz, 1H), 2.67–2.54 (m, 1H), CDCl3) δ: 8.06 (dd, J=8.4, 1.2Hz, 4H), 7.58 (t, J=7.6Hz,
2.50 (d, J=4.4Hz, 1H), 2.39–2.25 (m, 5H), 2.20–2.08 (m, 2H), 7.45 (t, J=7.8Hz, 4H), 6.31 (s, 2H), 5.60 (d, J=7.2Hz,
4H), 1.93–1.82 (m, 1H), 1.69 (s, 3H), 1.66 (s, 1H), 1.20 (s, 2H), 4.98 (d, J=7.6Hz, 2H), 4.88 (t, J=7.8Hz, 2H), 4.47 (dd,
3H), 1.17 (s, 3H). 13C-NMR (100MHz, CDCl3) δ: 203.9, 170.7, J=10.4, 6.8Hz, 2H), 4.29 (d, J=7.2Hz, 2H), 4.14 (d, J=8.4Hz,
167.1, 161.9, 146.5, 134.5, 133.7, 133.4, 132.5, 131.6, 130.1, 2H), 3.87 (d, J=7.2Hz, 2H), 2.68 (brs, 2H), 2.59–2.41 (m,
129.2, 128.6, 128.0, 84.4, 80.8, 79.1, 76.5, 76.4, 74.8, 72.3, 6H), 2.32–2.26 (m, 10H), 2.04 (s, 6H), 1.90–1.76 (m, 4H), 1.71
68.0, 58.7, 46.2, 42.7, 38.5, 35.7, 27.0, 22.6, 21.0, 15.7, 9.4. IR (quint, J=7.2Hz, 4H), 1.65 (s, 6H), 1.45–1.30 (m, 10H), 1.12 (s,
(neat) 3477, 2937, 1715, 1259cm−1. MS (FAB) m/z (rel inten- 6H), 1.10 (s, 6H). 13C-NMR (100MHz, CDCl3) δ: 204.2, 174.1,
sity) 677 (M+Na+, 5), 154 (100). HR-MS (FAB) m/z Calcd for 170.6, 167.0, 146.5, 133.6, 131.8, 130.1, 129.3, 128.6, 84.4, 80.7,
C34H38O11SNa (M+Na)+ 677.2033. Found 677.2032.
10-O-3-Furyl-10-deacetylbaccatin III
79.0, 76.4, 76.0, 74.9, 72.3, 67.8, 58.6, 46.1, 42.6, 38.7, 35.5,
34.2, 29.0, 28.8, 27.0, 24.8, 22.6, 21.0, 15.6, 9.4. IR (neat) 3503,
Colorless powder. mp 155–160°C. [α]D20 −83 (c=0.75, THF). 2932, 1716, 1242, 1070cm−1. MS (FAB) m/z (rel intensity)
1H-NMR (400MHz, CDCl3) δ: 8.14–8.08 (m, 3H), 7.62 (t, 1292 (M+Na+, 2), 154 (100). HR-MS (FAB) m/z Calcd for
J=7.6Hz, 1H), 7.52–7.46 (m, 3H), 6.78 (d, J=1.2Hz, 1H), C69H88O22Na (M+Na)+ 1291.5665. Found 1291.5660.
6.51 (s, 1H), 5.65 (d, J=7.2Hz, 1H), 5.00 (d, J=8.0Hz, 1H),
4.92 (brq, 1H), 4.57–4.47 (m, 1H), 4.32 (d, J=8.4Hz, 1H),
Acknowledgments This reseach was financially supported
4.16 (d, J=8.4Hz, 1H), 3.93 (d, J=6.8Hz, 1H), 2.65–2.52 (m, by a Grant-in-Aid for Scientific Research on Innovative Areas
2H), 2.36–2.26 (m, 5H), 2.11 (brs, 1H), 2.10 (s, 3H), 1.94–1.82 “Advanced Molecular Transformations by Organocatalysts”
(m, 1H), 1.69 (s, 3H), 1.65 (s, 1H), 1.17 (s, 3H), 1.15 (s, 3H). and Scientific Research (S) from the Ministry of Education,
13C-NMR (100MHz, CDCl3) δ: 204.0, 170.7, 167.1, 162.8, Culture, Sports, Science and Technology (MEXT) of Japan.
148.5, 146.5, 144.0, 133.7, 131.7, 130.1, 129.2, 128.6, 118.5,
109.9, 84.4, 80.8, 79.1, 76.4, 76.1, 74.8, 72.3, 68.0, 58.7, 46.2,
Conflict of Interest The authors declare no conflict of
42.7, 38.5, 35.7, 27.1, 22.6, 21.1, 15.7, 9.4. IR (neat) 3505, 2943, interest.