T. Takahashi et al.
FULL PAPERS
J
gem =17.4 Hz, J=4.3 Hz, 1H), 3.05 ppm (dd, Jgem =17.4 Hz, J=2.4 Hz,
(1JC,F =247 Hz), 158.7, 157.9, 155.8, 153.3ꢁ2, 141.5, 138.1, 137.3, 133.3,
132.6 (4JC,F =1.7 Hz), 132.5 (4JC,F =1.7 Hz), 129.4 (3JC,F =7.8 Hz), 129.1
(3JC,F =7.8 Hz), 128.5, 128.3, 128.1, 125.2, 115.6ꢁ2 (2JC,F =21.8 Hz), 107.4,
104.1, 101.1, 94.8, 94.0, 78.0, 69.6, 69.5, 68.6, 60.9, 56.4, 56.1, 26.2 ppm.
7aa (40%): Rf =0.68 (toluene:ethyl acetate=10:1); 1H NMR (400 MHz,
CDCl3): d=7.19–7.42 (m, 37H, aromatic), 6.73 (s, 2H), 6.38 (d, J=
1.9 Hz, 1H), 6.30 (d, J=1.9 Hz, 1H), 5.66 (brs, 1H), 4.95–5.04 (m, 9H),
4.90 (s, 2H, Bn), 4.80 (d, Jgem =11.6 Hz, 2H), 4.67 (d, Jgem =11.6 Hz, 2H),
1H); 13C NMR (67.8 MHz, CDCl3): d=164.8, 162.5 (1JC,F =247 Hz),
158.7, 157.9, 155.7, 153.5, 152.3, 142.5, 137.7, 137.3, 137.0, 136.5, 133.4,
132.5, 129.3 (3JC,F =8.4 Hz), 129.0 (3JC,F =8.4 Hz), 128.6, 128.5, 128.4,
128.2, 128.1, 128.0, 127.8, 127.6, 124.9, 115.5 (2JC,F =21.8 Hz), 109.2, 104.2,
101.1, 94.7, 94.0, 78.1, 75.1, 74.9, 71.1, 69.5, 69.4, 68.3, 55.9, 26.3 ppm.
6cb (56%): Rf =0.41 (hexane:ethyl acetate=2:1); 1H NMR (400 MHz,
CDCl3): d=7.27–7.42 (m, 21H, aromatic), 7.12 (t, J=8.7 Hz, 2H), 7.03
(t, J=8.7 Hz, 2H), 6.60 (s, 2H), 6.41 (d, J=1.9 Hz, 1H), 6.30 (d, J=
1.9 Hz, 1H), 5.66 (brs, 1H), 4.92–5.07 (m, 11H), 3.89 (s, 3H, h), 3.50 (s,
3.80 (s, 3H), 3.10 (dd, Jgem =17.9 Hz, J=4.3 Hz, 1H), 3.03 ppm (dd, Jgem
=
17.9 Hz, J=2.4 Hz, 1H); 13C NMR (67.8 MHz, CDCl3): d=164.8, 158.9ꢁ
2, 155.5, 152,8, 152.3, 142.7, 138.4, 137.7, 137.4, 136.8ꢁ2, 136.4, 133.3,
128.6, 128.5, 128.4ꢁ2, 128.3, 128.2, 128.1, 128.0ꢁ3, 127.8, 127.7, 127.5ꢁ2,
127.4, 124.9, 109.1, 106.6, 100.5, 94.2, 92.7, 77.9, 75.1, 75.0, 71.1, 71.0, 70.1,
68.2, 55.4, 26.0 ppm; HRMS (ESI-TOF): m/z (%) calcd for C72H66NO11:
1120.4636 [M+NH4]+; found: 1120.4679.
6H), 3.11 (dd,
Jgem =17.9 Hz, J=4.8 Hz, 1H), 3.04 ppm (dd, Jgem =
17.9 Hz, J=2.4 Hz, 1H); 13C NMR (67.8 MHz, CDCl3): d=164.9, 160.8,
158.8, 158.0, 155.8, 153.6, 152.3, 152.1, 144.0, 137.8, 137.1, 136.6, 133.3,
132.6, 129.4 (3JC,F =8.4 Hz), 129.3 (3JC,F =8.4 Hz), 128.7, 128.5, 128.2,
127.8ꢁ2, 127.6, 124.8, 115.6 (2JC,F =21.8 Hz), 110.4, 109.5, 104.2, 101.2,
94.9, 94.1, 78.2, 75.0, 71.2, 69.6, 69.5, 68.3, 61.1, 56.0, 26.4 ppm.
7ab (38%): Rf =0.66 (toluene:ethyl acetate=10:1); FTIR (neat): n˜ =
6cc (47%): Rf =0.35 (hexane:ethyl acetate=2:1); 1H NMR (400 MHz,
CDCl3): d=7.16–7.43 (m, 16H, aromatic), 7.04 (brt, J=8.7 Hz, 4H), 6.63
(s, 2H), 6.38 (d, J=1.9 Hz, 1H), 6.28 (d, J=1.9 Hz, 1H), 5.67 (brs, 1H,
f), 4.93–5.06 (m, 9H), 3.88 (s, 3H), 3.81 (s, 3H), 3.57 (s, 6H, j), 3.12 (dd,
2964, 1716, 1621, 1591, 1496, 1427, 1370, 1261, 1213, 1102, 1047, 801, 736,
697 cmÀ1 1H NMR (400 MHz, CDCl3): d=7.19–7.41 (m, 32H, aromatic),
;
6.71 (s, 2H), 6.38(d, J=2.4 Hz, 1H), 6.26 (d, J=2.4 Hz, 1H), 5.65 (brs,
1H), 4.94–5.06 (m, 9H), 4.75 (d, Jgem =11.6 Hz, 2H), 4.62 (d, Jgem
11.6 Hz, 2H, Bn), 3.80 (s, 3H), 3.77 (s, 3H), 3.05 (dd, Jgem =17.9 Hz, J=
4.3 Hz, 1H), 2.98 ppm (dd,
gem =17.9 Hz, J=2.4 Hz, 1H); 13C NMR
=
J
gem =17.9 Hz, J=4.9 Hz, 1H), 3.05 ppm (dd, Jgem =17.9 Hz, J=2.4 Hz,
1H); 13C NMR (67.8 MHz, CDCl3): d=165.0, 164.4, 158.8, 158.0, 155.8,
153.6, 153.2, 151.9, 144.1, 143.4, 137.8, 137.1, 136.6, 133.4, 132.6, 129.4
(3JC,F =8.4 Hz), 129.1 (3JC,F =7.8 Hz), 128.7ꢁ2, 128.5, 128.2ꢁ2, 127.9,
124.9, 115.6 (2JC,F =22.9 Hz), 109.3, 107.5, 104.2, 101.2, 94.9, 94.1, 78.1,
75.1, 71.2, 69.6, 69.5, 68.5, 61.0, 56.4, 56.1, 26.3 ppm.
J
(67.8 MHz, CDCl3): d=164.8, 159.1, 159.0, 155.6, 152,9, 152.1, 143.7,
138.5, 137.8, 137.0, 136.9, 136.5, 133.3, 128.7, 128.6, 128.4, 128.1ꢁ2,
127.8ꢁ2, 127.6ꢁ3, 127.5, 124.8, 109.2, 106.7, 100.6, 94.3, 92.8, 78.0, 75.2,
71.2, 71.0, 70.2, 68.3, 60.9, 55.5, 26.2 ppm; HRMS (ESI-TOF): m/z
(%)calcd for C66H62NO11: 1044.4323 [M+NH4]+; found: 1044.4332.
6cd (55%): Rf =0.37 (hexane:ethyl acetate=2:1); FTIR (neat): n˜ =2939,
7ac (39%): Rf =0.61 (toluene:ethyl acetate=10:1); 1H NMR (400 MHz,
CDCl3): d=7.17–7.43 (m, 27H, aromatic), 6.75 (s, 2H), 6.35 (d, J=
2.4 Hz, 1H), 6.24 (d, J=2.4 Hz, 1H), 5.65 (brs, 1H), 4.96–5.14 (m, 7H),
4.84 (d, Jgem =11.6 Hz, 2H), 4.71 (d, Jgem =11.6 Hz, 2H), 3.79 (s, 3H), 3.77
(s, 3H), 3.77 (s, 3H), 3.07 (dd, Jgem =17.9 Hz, J=4.3 Hz, 1H), 3.03 ppm
(dd, Jgem =17.9 Hz, J=3.4 Hz, 1H); 13C NMR (67.8 MHz, CDCl3): d=
165.0, 159.0ꢁ2, 155.5, 153,2, 152.9, 151.8, 137.8, 137.0, 136.9, 136.5, 133.4,
128.7, 128.6, 128.5, 128.4, 128.2ꢁ2, 128.1, 128.0, 127.9ꢁ2, 127.8, 127.6ꢁ3,
127.5, 124.9, 109.1, 107.3, 106.8, 100.5, 94.3, 92.8, 77.9, 75.2, 71.3, 71.0,
70.2, 68.5, 60.9, 56.3, 55.5, 26.1 ppm; HRMS (ESI-TOF): m/z (%) calcd
for C60H58NO11: 968.4010 [M+NH4]+; found: 968.4053.
1715, 1618, 1592, 1512, 1463, 1417, 1360, 1333, 1225, 1183, 1149, 1128,
1039, 826, 756, 734, 698 cmÀ1 1H NMR (400 MHz, CDCl3): d=7.28–7.43
;
(m, 14H, aromatic), 7.16 (s, 2H), 7.03–7.10 (m, 4H, aromatic), 6.67 (s,
2H), 6.33 (d, J=1.9 Hz, 1H), 6.25 (d, J=1.9 Hz, 1H), 5.66 (brs, 1H),
5.08 (s, 1H), 5.05 (s, 2H, Bn), 5.00 (s, 2H, Bn), 4.98 (s, 2H, Bn), 4.95 (s,
2H, Bn), 3.78 (s, 6H), 3.65 (s, 6H), 3.12 (dd, Jgem =17.9 Hz, J=4.8 Hz,
1H), 3.06 ppm (d, Jgem =17.9 Hz, 1H).
6da (48%): Rf =0.38 (hexane:ethyl acetate=2:1); 1H NMR (400 MHz,
CDCl3): d=7.26–7.36 (m, 21H, aromatic), 7.00–7.06 (m, 4H, aromatic),
6.60 (s, 2H), 6.39 (d, J=1.9 Hz, 1H), 6.30 (d, J=1.9 Hz, 1H), 5.66 (brs,
1H), 4.98–5.08 (m, 11H), 3.78 (s, 3H), 3.52 (s, 6H), 3.11 (dd, Jgem
17.4 Hz, J=3.9 Hz, 1H), 3.04 ppm (dd, Jgem =17.4 Hz, J=1.4 Hz, 1H).
=
7ad (41%): Rf =0.63 (toluene:ethyl acetate=10:1); 1H NMR (400 MHz,
CDCl3): d=d 7.18–7.45 (m, 27H, aromatic), 6.80 (s, 2H), 6.30(d,
J=2.4 Hz, 1H), 6.21 (d, J=2.4 Hz, 1H,), 5.63 (brs, 1H), 4.84–5.06 (m,
11H), 3.78 (s, 3H), 3.75 (s, 6H), 3.06 (dd, Jgem =17.9 Hz, J=4.3 Hz, 1H),
6db (53%): Rf =0.36 (hexane:ethyl acetate=2:1); 1H NMR (400 MHz,
CDCl3): d=7.28–7.40 (m, 16H, aromatic), 7.04 (t, J=8.7 Hz, 2H), 7.02
(t, J=8.7 Hz, 2H), 6.60 (s, 2H), 6.40 (d, J=1.9 Hz, 1H), 6.30 (d, J=
1.9 Hz, 1H), 5.67 (brs, 1H), 5.02 (s, 1H), 4.99–5.06 (m, 8H, Bn), 3.89 (s,
3H), 3.78 (s, 3H), 3.53 (s, 6H), 3.11 (dd, Jgem =17.9 Hz, J=4.3 Hz, 1H),
3.02 ppm (dd,
J
gem =17.9 Hz, J=2.4 Hz, 1H); 13C NMR (67.8 MHz,
CDCl3): d=165.3, 159.0, 155.5, 153,3, 152.9, 141.5, 138.5, 137.8, 137.4,
137.0ꢁ2, 133.5, 128.7, 128.6, 128.5, 128.3ꢁ2, 128.2, 128.1, 128.0, 127.9,
127.8, 127.6ꢁ2, 127.5, 125.3, 107.3, 106.9, 100.5, 92.8, 77.0, 75.2, 75.0, 71.5,
70.2, 68.7, 56.4, 55.5, 25.9 ppm; HRMS (ESI-TOF): m/z (%) calcd for
C60H58NO11: 968.4010 [M+NH4]+; found: 968.4009.
7ba (44%): Rf =0.66 (toluene:ethyl acetate=10:1); 1H NMR (400 MHz,
CDCl3): d=7.25–7.41 (m, 32H, aromatic), 6.71 (s, 2H), 6.35 (d, J=
1.9 Hz, 1H), 6.25 (d, J=1.9 Hz, 1H), 5.63 (brs, 1H), 5.04 (s, 1H, e),
3.05 ppm (dd,
J
gem =17.9 Hz, J=1.4 Hz, 1H); 13C NMR (67.8 MHz,
CDCl3): d=164.9, 162.6, 158.8, 158.0, 155.8, 153.2, 152.1, 144.0, 140.5,
138.1, 136.6, 133.1, 132.6, 129.4 (3JC,F =8.4 Hz), 129.1 (3JC,F =8.4 Hz),
128.7, 128.2, 127.8, 124.8, 115.6 (2JC,F =21.8 Hz), 109.4, 104.1, 101.2, 94.8,
94.1, 78.2, 71.1, 69.6, 69.5, 68.3, 61.1, 60.9, 56.0, 26.4 ppm.
6dc (49%): Rf =0.30 (hexane:ethyl acetate=2:1); 1H NMR (400 MHz,
CDCl3): d=7.26–7.40 (m, 11H, aromatic), 7.04 (t, J=8.7 Hz, 4H), 6.64
(s, 2H), 6.38 (d, J=2.4 Hz, 1H), 6.28 (d, J=2.4 Hz, 1H), 5.67 (brs, 1H),
4.99–5.08 (m, 7H), 3.88 (s, 3H), 3.81 (s, 3H), 3.79 (s, 3H), 3.60 (s, 6H),
3.12 (dd, Jgem =17.9 Hz, J=4.3 Hz, 1H), 3.06 ppm (dd, Jgem =17.9 Hz, J=
2.4 Hz, 1H); 13C NMR (67.8 MHz, CDCl3): d=165.0, 160.7, 158.7, 158.0,
155.8, 153.2, 151.8, 143.3, 138.0, 136.5, 133.2, 132.6 (4JC,F =2.2 Hz), 132.5
(4JC,F =2.2 Hz), 129.4 (3JC,F =8.4 Hz), 129.1 (3JC,F =8.4 Hz), 128.7, 128.3,
127.9, 124.9, 115.6ꢁ2 (2JC,F =21.2 Hz), 109.2, 107.5, 104.1, 101.2, 94.8,
94.1, 78.1, 71.1, 69.6, 69.5, 68.4, 61.0, 60.9, 56.4, 56.0, 26.4 ppm.
4.91–5.03 (m, 8H, Bn), 4.82 (d, Jgem =11.6 Hz, 2H, Bn), 4.71 (d, Jgem
11.6 Hz, 2H, Bn), 3.80 (s, 3H), 3.80 (s, 3H), 3.04 (dd, Jgem =17.9 Hz, J=
4.3 Hz, 1H), 2.98 ppm (dd,
gem =17.9 Hz, J=2.4 Hz, 1H); 13C NMR
=
J
(67.8 MHz, CDCl3): d=164.9, 159.0ꢁ2, 155.6, 152,7, 152.4, 142.8, 139.6,
137.5, 137.0, 136.9, 136.5, 133.1, 128.7, 128.6, 128.5, 128.3, 128.2, 128.1,
128.0, 127.9, 127.7, 127.6, 127.5, 127.4, 125.0, 109.2, 106.9, 100.6, 94.3,
92.8, 77.9, 75.1, 71.2, 71.1, 70.2, 68.3, 60.9, 55.5, 26.1 ppm; HRMS (ESI-
TOF): m/z (%) calcd for C66H62NO11: 1044.4323 [M+NH4]+; found:
1044.4333.
6dd (50%): Rf =0.31 (hexane:ethyl acetate=2:1); FTIR (neat): n˜ =3010,
7bb (49%): Rf =0.64 (toluene:ethyl acetate=10:1); 1H NMR (400 MHz,
CDCl3): d=7.25–7.46 (m, 27H, aromatic), 6.69 (s, 2H), 6.36 (d, J=
2.4 Hz, 1H), 6.25 (d, J=2.4 Hz, 1H), 5.63 (brs, 1H), 5.06 (s, 1H), 4.99–
5.03 (m, 6H), 4.77 (d, Jgem =11.6 Hz, 2H), 4.65 (d, Jgem =11.6 Hz, 2H),
3.80 (s, 3H), 3.80 (s, 3H), 3.78 (s, 3H), 3.03 (dd, Jgem =17.9 Hz, J=4.3 Hz,
1H), 2.97 ppm (dd, Jgem =17.9 Hz, J=2.4 Hz, 1H); 13C NMR (67.8 MHz,
CDCl3): d=164.8, 159.1ꢁ2, 155.6, 152,7, 152.1, 143.9, 139.7, 137.1, 136.9,
136.6, 133.1, 128.7, 128.5ꢁ2, 128.1, 127.8ꢁ2, 127.6, 127.5ꢁ2, 127.4, 124.8,
2939, 2841, 1715, 1621, 1593, 1512, 1463, 1417, 1361, 1334, 1228, 1183,
1149, 1129, 1040, 1014, 827, 756, 699, 506 cmÀ1 1H NMR (400 MHz,
;
CDCl3): d=7.28–7.44 (m, 9H, aromatic), 7.16 (s, 2H), 7.08 (t, J=8.7 Hz,
2H), 7.04 (t, J=8.7 Hz, 2H), 6.68 (s, 2H, d), 6.33 (d, J=2.4 Hz, 1H), 6.25
(d, J=2.4 Hz, 1H), 5.66 (brs, 1H), 5.08 (s, 1H), 5.05 (s, 2H), 5.00 (s,
2H), 4.98 (s, 2H), 3.80 (s, 3H), 3.78 (s, 6H), 3.69 (s, 6H), 3.12 (dd, Jgem
=
18.4 Hz, J=4.8 Hz, 1H), 3.06 ppm (dd, Jgem =18.4 Hz, J=2.9 Hz, 1H);
13C NMR (67.8 MHz, CDCl3): d=165.2, 162.6 (1JC,F =247 Hz), 162.5
2240
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Chem. Asian J. 2010, 5, 2231 – 2248