´
Z. Zalan et al. / Tetrahedron 59 (2003) 9117–9125
9124
C19H23N2O3P requires C, 63.68; H, 6.47; N, 7.82%]; nmax
3161, 1513, 1211, 1120, 989 cm21; dH (400 MHz, CDCl3)
7.89 (2H, d, J¼7.7 Hz, Ph), 7.49 (1H, t, J¼7.3 Hz, Ph), 7.44
(2H, t, J¼7.5 Hz, Ph), 6.61 (1H, s, H8), 6.50 (1H, s, H-11),
4.39 (1H, dd, J¼7.9, 6.6 Hz, H-11b), 3.86 (3H, s, OCH3),
3.81 (3H, s, OCH3), 3.62 (1H, dt, J¼12.1, 4.8 Hz, H-6eq),
3.29–3.49 (2H, m, H-2ax, H-2eq), 3.18 (1H, ddd, J¼12.1,
8.3, 3.9 Hz, H-6ax), 2.94 (1H, ddd, J¼15.6, 8.3, 4.4 Hz,
H-7ax), 2.73 (1H, dt, J¼15.6, 4.6 Hz, H-7eq), 2.00–2.11
(2H, m, H-1ax, H-1eq); dC (100.03 MHz, CDCl3) 148.1,
147.9, 133.8, 131.7, 131.6, 128.9 (2C), 127.8, 112.1, 109.5,
56.6, 56.4, 56.3, 41.9, 39.0, 34.1, 29.9; MS m/z 359
[Mþ1]þ.
148.0, 144.7, 133.3, 132.8, 131.7, 129.5, 129.3, 128.4,
127.4, 125.7, 125.0, 112.2, 108.9, 56.5, 56.3, 55.0, 49.6,
41.7, 35.3, 29.0; MS m/z 435 [Mþ1]þ.
Compounds 7c–8c¼27:73. Eluent: EtOAc–MeOH¼9:1.
Compound 7c. Beige solid; yield: 0.45 g (12%), mp 130–
131.58C (EtOAc). [Found: C, 64.28; H, 6.51; N, 7.45.
C20H25N2O3P requires C, 64.51; H, 6.77; N, 7.52%]; nmax
1517, 1231, 1123, 992, 719 cm21; dH (400 MHz, CDCl3)
7.72 (2H, d, J¼7.34 Hz, Ph), 7.40–7.51 (3H, m, Ph), 6.58
(1H, s, H-8), 6.55 (1H, s, H-11), 4.46 (1H, dd, J¼4.0,
10.1 Hz, H-11b), 3.84 (3H, s, OCH3), 3.83 (3H, s, OCH3),
3.62 (1H, dt, J¼3.9, 11.6 Hz, H-6eq), 3.46 (1H, dt, J¼5.3,
11.6 Hz, H-2ax), 3.25 (1H, dt, J¼4.2, 11.6 Hz, H-2eq),
2.82–3.0 (2H, m, H-6ax, H-7ax), 2.69 (3H, s, NCH3), 2.63
(1H, dt, J¼3.7, 15.2 Hz, H-7eq), 2.14–2.3 (2H, m, H-1ax,
H-1eq); dC (100.03 MHz, CDCl3) 148.1, 147.9, 133.4, 131.6
(2C), 128.9, 128.7, 127.8, 112.1, 109.2, 56.4, 56.2 (2C),
50.8, 39.4, 35.9, 34.1, 29.9; MS m/z 373 [Mþ1]þ.
Compound 8a. Pale yellow solid; yield: 0.64 g (18%), mp
193–196.58C (iPr2O–EtOAc). [Found: C, 63.90, H, 6.53;
N, 7.78. C19H23N2O3P requires C, 63.68; H, 6.47; N,
7.82%]; nmax 1509, 1255, 1185, 1121, 991 cm21; dH
(400 MHz, CDCl3) 7.90 (2H, d, J¼7.5 Hz, Ph), 7.48 (1H,
t, J¼7.3 Hz, Ph), 7.41 (2H, t, J¼7.5 Hz, Ph), 6.67 (1H, s,
H-11), 6.53 (1H, s, H-8), 6.49 (1H, dd, J¼11.4, 3.3 Hz,
H-11b), 3.87 (3H, s, OCH3), 3.84 (3H, s, OCH3), 3.54 (1H, t,
J¼11.2 Hz, H-2ax), 3.29–3.41 (2H, m, H-2eq, H-6eq), 2.98
(1H, dt, J¼12.3, 3.1 Hz, H-6ax), 2.57 (1H, ddd, J¼15.6,
11.9, 5.1 Hz, H-7ax), 2.42–2.50 (1H, m, H-1eq), 2.38 (1H,
d, J¼15.6 Hz, H-7eq), 1.91–2.04 (1H, m, H-1ax); dC
(100.03 MHz, CDCl3) 148.0 (2C), 133.5, 133.1, 131.9,
129.5, 128.6, 127.4, 112.2, 109.1, 56.5, 56.3, 55.3, 41.1,
40.2, 35.4, 29.1; MS m/z 359 [Mþ1]þ.
Compound 8c. Beige needles; yield: 1.05 g (28%), mp 176–
1778C (iPr2O–EtOAc). [Found: C, 64.47; H, 6.48; N, 7.59.
C20H25N2O3P requires C, 64.51; H, 6.77; N, 7.52%]; nmax
2829, 1513, 1254, 1129, 1063 cm21; dH (400 MHz, CDCl3)
7.89 (2H, d, J¼7.5 Hz, Ph), 7.49 (1H, t, J¼7.2 Hz, Ph), 7.43
(2H, t, J¼7.5 Hz, Ph), 6.68 (1H, s, H-11), 6.53 (1H, s, H-8),
4.69 (1H, d, J¼11.3 Hz, H-11b), 3.88 (3H, s, OCH3), 3.84
(3H, s, OCH3), 3.54 (1H, dt, J¼3.5, 11.2 Hz, H-2ax), 3.34
(1H, dd, J¼2.0, 5.1, 12.5 Hz, H-6eq), 3.08 (1H, dt, J¼4.4,
11.2 Hz, H-2eq), 2.97 (1H, dt, J¼3.1, 12.5 Hz, H-6ax),
2.50–2.61 (4H, m, NCH3, H-7ax), 2.42–2.49 (1H, m,
H-1eq), 2.35 (1H, d, J¼15.6 Hz, H-7eq), 1.97–2.11 (1H, m,
H-1ax); dC (100.03 MHz, CDCl3) 148.0 (2C), 133.5, 132.3,
131.7, 129.3, 128.5, 127.3, 112.1, 109.1, 56.5, 56.2, 54.6,
49.1, 41.4, 35.7, 35.3, 29.1; MS m/z 373 [Mþ1]þ.
Compounds 7b–8b¼29:71. Eluent: EtOAc–MeOH¼9:1.
Compound 7b. Pale yellow solid; yield: 0.62 g (14%), mp
155–1628C (iPr2O–EtOAc). [Found: C, 68.92; H, 6.04; N,
6.37. C25H27N2O3P requires C 69.11, H 6.26, N 6.45%];
nmax 1519, 1235, 1133, 696, 509 cm21; dH (400 MHz,
CDCl3) 7.64 (2H, d, J¼7.7 Hz, Ph), 7.37–7.44 (3H, m, Ph),
7.34 (2H, t, J¼7.5 Hz, Ph), 7.25 (2H, t, J¼7.7 Hz, Ph), 7.03
(1H, t, J¼7.3 Hz, Ph), 6.63 (1H, s, H-11), 6.57 (1H, s, H-8),
4.56 (1H, dd, J¼9.2, 6.2 Hz, H-11b), 3.79–3.92 (7H, m,
H2ax, OCH3), 3.73 (1H, dt, J¼12.3, 4.0 Hz, H-2eq), 3.63
(1H, dt, J¼12.5, 5.0 Hz, H-6eq), 3.26 (1H, ddd, J¼12.3, 7.9,
4.0 Hz, H-6ax), 3.00 (1H, ddd, J¼15.0, 7.9, 4.2 Hz, H-7ax),
2.76 (1H, dt, J¼15.6, 4.8 Hz, H-7eq), 2.28–2.40 (2H, m,
H-1ax, H-1eq); dC (100.03 MHz, CDCl3) 148.3, 148.0,
145.4, 132.9, 131.9, 131.7, 129.3, 128.9, 128.7, 127.8,
124.1, 123.3, 112.2, 109.2, 56.5 (2C), 56.3, 49.9, 39.4, 34.1,
29.9; MS m/z 435 [Mþ1]þ.
Compounds 7d–8d¼,100:, 0. Eluent: EtOAc–
MeOH¼9:1.
Compound 7d. White solid; yield: 1.64 g (44%), mp 188–
1928C (iPr2O–EtOAc). [Found: C, 64.42; H, 6.73; N, 7.38.
C20H25N2O3P requires C, 64.51; H, 6.77; N, 7.52%]; nmax
1513, 1193, 1123, 995, 699 cm21; dH (400 MHz, CDCl3)
7.90 (2H, d, J¼8.0 Hz, Ph), 7.50 (1H, t, J¼7.2 Hz, Ph), 7.44
(2H, t, J¼7.5 Hz, Ph), 6.65 (1H, s, H-11), 6.51 (1H, s, H-8),
3.92 (1H, d, J¼9.2 Hz, H-11b), 3.86 (3H, s, OCH3), 3.81
(3H, s, OCH3), 3.76 (1H, ddd, J¼4.6, 5.9, 12.3 Hz, H-6eq),
3.47 (1H, dd, J¼4.6, 12.5 Hz, H-2eq), 3.26 (1H, ddd, J¼4.4,
7.9, 12.3 Hz, H-6ax), 2.86–2.99 (2H, m, H-2ax, H-7ax),
2.78 (1H, dt, J¼5.1, 15.4 Hz, H-7eq), 2.10–2.18 (1H, m,
H-1ax), 0.96 (3H, d, J¼6.8 Hz, Me-1); dC (100.03 MHz,
CDCl3) 148.6, 147.1, 133.3, 132.2, 132.1, 129.3 (2C),
127.8, 112.4, 112.2, 61.6, 56.7, 56.5, 48.8, 39.6, 37.6, 30.4,
18.3; MS m/z 373 [Mþ1]þ.
Compound 8b. White solid; yield: 1.14 g (26%), mp 194–
1968C (iPr2O–EtOAc). [Found C, 69.01; H, 5.96; N, 6.42.
C25H27N2O3P requires C 69.11, H 6.26, N 6.45%]; nmax
2920, 1514, 1375, 1207, 1122 cm21; dH (400 MHz, CDCl3)
7.77 (2H, d, J¼7.7 Hz, Ph), 7.39 (1H, t, J¼7.3 Hz, Ph), 7.31
(2H, t, J¼7.7 Hz, Ph), 7.09–7.18 (4H, m, Ph), 6.96–7.04
(1H, m, Ph), 6.71 (1H, s, H-11), 6.54 (1H, s, H-8), 4.84 (1H,
dd, J¼4.6, 10.5 Hz, H-11b), 4.00 (1H, dt, J¼3.3, 12.1 Hz,
H-2ax), 3.89 (3H, s, OCH3), 3.85 (3H, s, OCH3), 3.63 (1H,
dt, J¼4.4, 12.1 Hz, H-2eq), 3.53 (1H, ddd, J¼2.0, 5.3,
12.5 Hz, H-6eq), 3.06 (1H, dt, J¼3.3, 12.5 Hz, H-6ax),
2.64–2.72 (1H, m, H-1eq), 2.57 (1H, ddd, J¼5.3, 12.1,
15.6 Hz, H-7ax), 2.40 (1H, d, J¼15.6 Hz, H-7eq), 2.17–
2.29 (1H, m, H-1ax); dC (100.03 MHz, CDCl3) 148.1,
Compounds 7e–8e¼57:43. Eluent: EtOAc–MeOH¼9:1.
Compound 7e. White needles; yield: 0.52 g (14%), mp 180–
1848C (iPr2O–EtOAc). [Found: C, 64.71; H, 6.56; N, 7.42.
C20H25N2O3P requires C, 64.51; H, 6.77; N, 7.52%]; nmax
3146, 1513, 1211, 1133, 988 cm21; dH (400 MHz, CDCl3)
7.8 (2H, d, J¼7.7 Hz, Ph), 7.40–7.51 (3H, m, Ph), 6.59 (1H,