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1.14 (s, 3H), 1.24 (s, 3H), 1.68 (s, 3H), 1.77 (s, 3H), 1.92
(m, 1H), 2.24 (m, 5H), 2.33 (s, 3H), 2.51 (m, 1H), 3.53
(s, 3H), 3.73 (d, J=6.7 Hz, 1H), 4.24 (dd, 2H), 4.39 (m,
1H), 4.92 (d, J=7.0 Hz, 1H), 5.58 (m, 1H), 5.65 (d,
J=7.5 Hz, 1H), 6.14 (t, J=7.0 Hz, 1H), 6.25 (s, 1H),
6.36 (d, J=8.7 Hz, 1H), 7.11–7.42 (m, 10H), 7.51 (t,
J=7.2 Hz, 2H), 7.62 (t, J=7.2 Hz, 1H), 8.10 (d, J=7.2
Hz, 2H); 13C NMR (63 MHz, CDCl3) d 10.0, 15.3, 22.0,
23.0, 23.8, 27.5, 35.9, 36.0, 42.1, 44.5, 44.7, 45.8, 55.0,
58.7, 73.5, 73.6, 74.0, 75.5, 76.5, 77.1, 79.7, 82.6, 127.8,
128.2, 128.5, 129.0, 129.1, 129.2, 129.5, 129.8, 130.0,
130.8, 134.2, 134.9, 135.2, 138.5, 143.7, 167.4, 170.6,
171.2, 172.8, 173.8, 204.8. Anal. calcd for C48H53NO14:
C, 66.42; H, 6.15. Found: C, 66.56; H, 5.96.
128.7, 128.9, 129.0, 130.0, 133.2, 133.7, 137.8, 141.9,
165.9, 167.0, 170.4, 171.3, 172.7, 203.6. Anal. calcd for
C47H50ClNO14: C, 63.55; H, 5.96; N, 1.58 Found: C,
63.56, H, 6.01; N, 1.53.
30-N-Debenzoyl-30-N-(4-methoxybenzoyl)paclitaxel (17j).
Yield 96%; mp 158–159 ꢁC; [a]D20 À42.2 (c 0.9, CHCl3);
1H NMR (250 MHz, CDCl3) d 1.13 (s, 3H), 1.23 (s, 3H),
1.67 (s, 3H), 1.78 (s, 3H), 1.92 (m, 1H), 2.23 (s, 3H), 2.30
(m, 2H), 2.37 (s, 3H), 2.54 (m, 1H), 3.81 (m, 3H), 4.23
(dd, 2H), 4.38 (dd, J1=8.2 Hz, J2=7.0 Hz, 1H), 4.77 (d,
J=2.5 Hz, 1H), 4.93 (d, J=8.0 Hz, 1H), 5.65 (d, J=7.0
Hz, 1H), 5.76 (dd, J1=8.7 Hz, J2=2.4 Hz, 1H), 6.20
(m, 2H), 6.84–6.95 (m, 3H), 7.25–7.77 (m, 8H), 7.95 (d,
J=8.7 Hz, 2H), 8.11 (d, J=7.2 Hz, 1H); 13C NM R
(63 MHz, CDCl3) d 9.6, 14.8, 20.8, 21.8, 22.6, 26.8, 35.7,
43.1, 45.6, 54.1, 54.4, 58.6, 72.2, 72.3, 73.3, 74.9, 75.5,
76.5, 79.0, 81.6, 84.4, 113.6, 113.9, 125.7, 127.0, 128.3,
128.7, 128.9, 129.0, 130.2, 132.2, 133.1, 133.7, 136.1,
142.0, 166.9, 170.4, 171.3, 172.7, 203.6. Anal. calcd for
C48H53NO15: C, 65.22; H, 6.04; N, 1.58 Found: C,
65.32, H, 6.01; N, 1.51.
30-N-Debenzoyl-30-N-cinnamoylpaclitaxel (17g). Yield
78%; mp 149–150 ꢁC; H NMR (250 MHz, CDCl3) d
1
1.15 (s, 3H), 1.24 (s, 3H), 1.69 (s, 3H), 1.84 (m, 4H), 2.23
(s, 3H), 2.31 (m, 2H), 2.39 (s, 3H), 2.51 (m, 1H), 3.75
(m, 1H), 3.80 (d, J=6.7 Hz, 1H), 4.24 (dd, 2H), 4.39 (m,
1H), 4.75 (s, 1H), 4.94 (d, J=7.0 Hz, 1H), 5.70 (m, 1H),
6.26 (m, 2H), 6.38 (d, J=8.7 Hz, 1H), 6.48 (d, J=7.2
Hz, 1H), 6.52 (d, J=8.8 Hz, 1H), 7.30–7.62 (m, 14H),
8.16 (d, J=7.2 Hz, 2H); 13C NMR (63 MHz, CDCl3) d
10.0, 15.7, 22.0, 23.0, 23.8, 27.5, 35.9, 36.0, 44.3, 45.8,
55.3, 58.5, 73.5, 73.6, 74.0, 75.5, 77.1, 77.6, 79.7, 85.2,
95.6, 120.4, 127.8, 128.2, 128.7, 129.0, 129.2, 129.5,
129.8, 131.2, 132.0, 134.2, 134.9, 135.2, 138.5, 143.4,
143.7, 167.4, 170.6, 171.2, 172.8, 173.8, 204.8. Anal.
calcd for C49H53NO14: C, 66.88; H, 6.07. Found: C,
66.85; H, 6.02.
30 -N-Debenzoyl-30 -N-(3,4-dimethoxybenzoyl)paclitaxel
(17k). Yield 78%; mp 148–149 ꢁC; [a]D20 À36.5 (c 1.15,
1
CHCl3); H NMR (250 MHz, CDCl3) d 1.12 (s, 3H),
1.26 (s, 3H), 1.67 (s, 3H), 1.86 (s, 3H), 1.90 (m, 1H), 2.22
(s, 3H), 2.35 (m, 2H), 2.42 (s, 3H), 2.54 (m, 1H), 3.64 (s,
3H), 3.69 (d, J=7.0 Hz, 1H), 3.88 (s, 3H), 4.24 (dd, 2H),
4.40 (dd, J1=8.2 Hz, J2=7.0, 1H), 4.80 (d, J=2.2 Hz,
1H), 4.93 (d, J=8.0 Hz, 1H), 5.65 (d, J=7.0 Hz, 1H),
5.81 (dd, J1=8.7 Hz, J2=2.2 Hz, 1H), 6.23 (m, 2H),
6.81 (d, J=8.2 Hz, 1H), 6.96 (d, J=8.7 Hz, 1H), 7.25–
7.66 (m, 10H), 8.16 (d, J=7.2 Hz, 1H); 13C NM R
(CDCl3) d 9.6, 14.8, 20.8, 21.8, 22.7, 25.8, 35.5, 43.1,
45.5, 54.8, 55.7, 56.0, 56.5, 72.2, 72.3, 73.3, 74.9, 75.5,
76.5, 79.1, 81.0, 84.4, 110.0, 110.8, 119.2, 126.1, 126.9,
128.2, 128.7, 129.0, 129.1, 130.2, 133.1, 133.7, 138.0,
142.0, 149.1, 152.1, 167.0, 170.4, 171.3, 172.7, 203.6.
Anal. calcd for C49H55NO16: C, 69.26; H, 6.48; N, 1.65
Found: C, 69.38, H, 6.54; N, 1.58.
30-N-Debenzoyl-30-N-(4-methylbenzoyl)paclitaxel (17h).
Yield 89%; mp 142–143 ꢁC; [a]2D0 À43.0 (c 1.00,
1
CHCl3); H NMR (250 MHz, CDCl3) d 1.12 (s, 3H),
1.22 (s, 6H), 1.67 (s, 3H), 1.78 (s, 3H), 1.88 (m, 1H), 2.22
(s, 3H), 2.29 (m, 2H), 2.35 (s, 3H), 2.37 (s, 3H), 2.54 (m,
1H), 3.78 (d, J=7.0 Hz, 1H), 3.88 (s, 3H), 4.24 (dd, 2H),
4.36 (dd, J1=8.2 Hz, J2=7.0 Hz, 1H), 4.77 (d, J=2.2
Hz, 1H), 4.92 (d, J=8.0 Hz, 1H), 5.65 (d, J=7.0 Hz,
1H), 5.76 (dd, J1=8.7 Hz, J2=2.2 Hz, 1H), 6.20 (m,
2H), 7.00 (d, J=8.7 Hz, 1H), 7.15–7.69 (m, 12H), 8.11
(d, J=7.2 Hz, 1H); 13C NMR (63 MHz, CDCl3) d 9.5,
14.8, 20.9, 21.6, 22.6, 26.8, 29.6, 35.6, 43.1, 45.5, 55.0,
56.5, 72.2, 73.3, 74.9, 75.5, 76.5, 79.0, 81.1, 84.4, 120.0,
127.3, 128.3, 128.7, 129.0, 129.1, 129.3, 130.2, 133.1,
133.7, 138.0, 142.0, 143.5, 166.9, 170.4, 171.8, 172.7,
203.6. Anal. calcd for C48H53NO14: C, 66.42; H, 6.15;
N, 1.61 Found: C, 66.45, H, 6.11; N, 1.59.
30-N-Debenzoyl-30-N-(4-ethylbenzoyl)paclitaxel (17m).
Yield 95%; mp 146–147 ꢁC; [a]2D0 À45.3 (c 0.75,
1
CHCl3); H NMR (250 MHz, CDCl3) d 1.13 (s, 3H),
1.24 (m, 6H), 1.68 (s, 3H), 1.79 (s, 3H), 1.84 (m, 1H),
2.23 (s, 3H), 2.30 (m, 2H), 2.38 (s, 3H), 2.64 (m, 3H),
3.78 (d, J=5.7 Hz, 1H), 4.24 (dd, 2H), 4.40 (dd, J1=8.2
Hz, J2=5.2 Hz, 1H), 4.77 (d, J=2.2 Hz, 1H), 4.94 (d,
J=6.5 Hz, 1H), 5.66 (d, J=6.0 Hz, 1H), 5.76 (dd,
J1=7.5 Hz, J2=2.2 Hz, 1H), 6.22 (m, 2H), 6.97 (d,
J=7.0 Hz, 1H), 7.20–7.67 (m, 12H), 8.11 (d, J=7.2 Hz,
2H); 13C NMR (63 MHz, CDCl3) d 9.4, 14.7, 20.7, 21.7,
22.5, 26.7, 28.6, 35.5, 35.6, 43.0, 45.5, 54.9, 58.5, 72.1,
72.2, 73.2, 74.9, 75.5, 78.9, 81.0, 84.3, 99.9, 126.9, 127.0,
128.0, 128.2, 128.9, 129.1, 130.1, 130.9, 133.0, 133.6,
133.9, 138.0, 148.7, 166.9, 170.3, 171.3, 172.6, 203.6.
Anal. calcd for C49H55NO14: C, 66.74; H, 6.24; N, 1.59
Found: C, 66.75, H, 6.30; N, 1.55.
30-N-Debenzoyl-30-N-(4-chlorobenzoyl)paclitaxel (17i).
Yield 81%; mp 159–160 ꢁC; [a]2D0 À48.6 (c 1.05,
1
CHCl3); H NMR (250 MHz, CDCl3) d 1.13 (s, 3H),
1.24 (s, 3H), 1.67 (s, 3H), 1.77 (s, 3H), 1.84 (m, 1H), 2.23
(s, 3H), 2.30 (m, 2H), 2.36 (s, 3H), 2.56 (m, 1H), 3.78 (d,
J=7.0 Hz, 1H), 4.22 (dd, 2H), 4.38 (dd, J1=8.2 Hz,
J2=7.0 Hz, 1H), 4.77 (d, J=2.2 Hz, 1H), 4.93 (d, J=8.7
Hz, 1H), 5.65 (d, J=7.0 Hz, 1H), 5.76 (dd, J1=8.7
Hz, J2=2.2 Hz, 1H), 6.21 (m, 2H), 6.28 (s, 1H), 7.02
(d, J=8.7 Hz, 1H), 7.20–7.90 (m, 12H), 8.12 (d,
J=7.2 Hz, 2H); 13C NMR (CDCl3) d 9.5, 14.8, 20.8,
21.7, 22.6, 26.8, 35.6, 43.2, 45.6, 55.0, 58.6, 72.2, 72.3,
73.1, 74.8, 75.5, 76.5, 79.0, 81.5, 84.3, 127.0, 128.5,
30-N-Debenzoyl-30-N-(4-propylbenzoyl)paclitaxel (17n).
Yield 95%; mp 145–146 ꢁC; [a]D20 À41.0 (c 0.9, CHCl3);
1H NMR (250 MHz, CDCl3) d 1.13 (s, 3H), 1.22 (s, 6H),