1298
W. Hatton et al. / C. R. Chimie 13 (2010) 1284–1300
5b = 8.5 Hz, J3–4 = 6.3 Hz, J4–5a = 2.6 Hz); 6.88 (d, 1 H, 13-H,
J = 7.9 Hz); 6.98 (dt, 1 H, 11-H, J = 7.6 Hz, J = 0.9 Hz); 7.22
(dt, 1 H, 12-H, J = 7.8 Hz, J = 1.2 Hz); 7.32 (d, 2 H, 20-H,
J = 8.3 Hz); 7.47 (dd, 1 H, 10-H, J = 7.6 Hz, J = 0.7 Hz); 7.50 (s,
1 H, 17-H) 8.20 (d, 1 H, 19-H, J = 8.3 Hz). 13C-NMR
(100.61 MHz, CDCl3): ꢂ4.9 + ꢂ4.8 + ꢂ4.7 + ꢂ4.3 + ꢂ4.2 +
ꢂ4.0 (2 ꢁ 6-C + 2 ꢁ 6’-C + 2 ꢁ 6’’-C); 18.1 + 18.5 (7-C + 7’-
C + 7’’-C); 24.0 + 24.1 + 24.2 (8-C + 8’-C + 8’’-C); 40.9 (5-C);
67.8 (3-C); 69.3 (4-C); 72.7 (1-C); 73.4 (2-C); 109.0 (13-C);
118.9 (10-C); 121.8 (12-C); 127.0 (20-C); 129.9 (11-C);
132.1 (9-C); 132.3 (19-C); 137.0 (17-C); 152.0 (15-C);
169.4(16-C). MS (ESI+): 744 [M + Na]+.
layers were then evaporated under reduced pressure. The
residue was purified with Biotage SP1TM (n-hexane/
acetone from 88/12 to 0/100; SNAP 10 g column) to give
16 in a Z/E 40/60 mixture (11.6 mg, 74%) as a yellow solid.
Rf = 0.3 + 0.2 (Hexane/Acetone 5/5). 1H-NMR (400 MHz,
CD3OD): 1.46 (d, 6 H, 23-H Z-isomer, J = 6.9 Hz); 1.48 (d, 6
H, 23-H, Z-isomer, J = 6.9 Hz); 1.94–2.02 (m, 1 H, 5a-H);
2.69 (ddd, 1 H, 5b-H, Jgem = 14.2 Hz, J = 8.4 Hz, J = 5.6 Hz);
3.15 (sp, 1 H, 19-H, J = 6.9 Hz); 4.31–4.38 (m, 1 H, 1-H); 4.64
(dd, 1 H, 3-H, J = 15.5 Hz, J = 7.0 Hz); 4.81 (dd, 1 H, 2-H,
J = 8.8 Hz, J = 4.0 Hz); 4.85–4.93 (m, 1 H, 4-H); 7.03–7.12
(m, 1 H, 9-H Z-isomer); 7.18–7.26 (m, 2 H, 9-H Z-
isomer + 10-H E-isomer); 7.25–7.31 (d, 1 H, 10-H E-isomer,
J = 8.0 Hz); 7.40–7.51 (m, 2 H, Ar-H); 7.52–7.60 (m, 1 H, Ar-
H); 7.76–7.92 (m, 3 H, Ar-H); 8.44 (d, 1 H, 14-H Z-isomer,
J = 8.3 Hz). 13C-NMR (100.61 MHz, CD3OD): 24.1 + 24.2 (20-
C); 35.4 + 35.5 (19-C); 40.2 (5-C); 67.8 + 67.8 (3-C); 69.8 (4-
C); 71.0 + 71.1 (1-C); 73.1 (2-C); 109.9 + 110.6 (10-C);
118.9 (10-C); 129.7 (Ar-CH); 130.7 + 130.8 (Ar-CH); 133.3
(CIV); 133.5 (Ar-CH); 133.6 (CIV); 138.3 (Ar-CH); 138.5 (Ar-
5.28.2. 15E (Fig. 2. – S34)
CH);
168.3 + 170.7 (16-C). MS (ESI+): 744 [M + Na]+. HRMS:
23H25NO4Na: calcd. 402.16758; found 402.16725.
143.6 + 145.6
(CIV);
152.6 + 153.2
(12-C);
C
Rf = 0.4 (Hexane/EtOAc 6/4). 1H-NMR (400 MHz, CDCl3):
ꢂ0.26 + ꢂ0.25 + ꢂ0.11 + ꢂ0.06 + 0.10 + 0.12 (6 s, 6 ꢁ 3 H,
6 ꢁ 6-H + 6 ꢁ 6’-H + 6 ꢁ 6’’-H); 0.69 + 0.76 + 0.98 (3 s, 3 ꢁ 9
H, 9 ꢁ 8-H + 9 ꢁ 8’-H + 9 ꢁ 8’’-H); 1.30 (d,
6
H, 23-H,
H, 5a-H, Jgem = 14.1 Hz, J4–
5a = 2.9 Hz, J1–5a = 2.6 Hz); 2.32 (ddd, H, 5b-H,
J = 6.9 Hz); 1.73 (ddd,
1
1
Jgem = 14.1 Hz, J4–5b = 8.6 Hz, J1–5b = 4.4 Hz); 2.98 (sp, 1 H,
22-H, J = 6.9 Hz); 4.07–4.11 (m, 1 H, 1-H); 4.42 (dd, 1 H, 3-H,
J2–3 = 9.0 Hz, J3–4 = 6.3 Hz); 4.62 (dd, 1 H, 2-H, J2–3 = 9.0 Hz,
J1–2 = 3.9 Hz); 4.88 (ddd, 1 H, 4-H, J4–5b = 8.6 Hz, J3–4 = 6.3 Hz,
J4–5a = 2.9 Hz); 6.84 (dt, 1 H, 11-H, J = 7.6 Hz, J = 1.0 Hz); 6.91
(d, 1 H, 13-H, J = 8.1 Hz); 7.22 (dt, 1 H, 12-H, J = 7.8 Hz;
J = 1.2 Hz); 7.32 (d, 2 H, 20-H, J = 8.4 Hz); 7.63 (d, 1 H, 19-H,
J = 7.9 Hz); 7.71 (d, 1 H, 10-H, J = 6.6 Hz); 7.74 (s, 1 H, 17-H).
13C-NMR (100.61 MHz, CDCl3): ꢂ4.9 + ꢂ4.8 + ꢂ4.7 + ꢂ4.3 +
ꢂ4.2 + ꢂ4.0 (2 ꢁ 6-C + 2 ꢁ 6’-C + 2 ꢁ 6’’-C); 18.1 + 18.5 (7-
C + 7’-C + 7’’-C); 25.9 + 26.0 + 26.3 (8-C + 8’-C + 8’’-C); 41.0
(5-C); 67.9 (3-C); 69.7 (4-C); 72.6 (1-C); 73.9 (2-C); 109.4
(13-C); 121.5 (12-C); 122.9 (10-C); 127.0 (20-C); 129.9 (11-
C); 130.0 (19-C); 132.9 (9-C); 136.9 (17-C); 151.2 (15-C);
169.4(16-C). MS (ESI+): 744 [M + Na]+.
5.30. (ꢃ)-2-chloro-N-((1R,2S,3R,5S)-2,3,5-tris(tert-
butyldimethylsilyloxy)cyclopentyl)aniline 19 (Fig. 2. – S36)
TBDMSOTf (302
mL, 1.314 mmol) was added at 0 8C to a
solution of 2,6-lutidine (218
ml, 1.877 mmol), 7b (224 mg,
0.626 mmol) and 8b (224 mg, 0.626 mmol) in dry THF
(4 mL). The solution was stirred for 2 h, the solvent was
removed under reduced pressure and the residue was taken
up in Et2O (4 mL). The organic layer was washed two times
with water, dried over Na2SO4, filtered and evaporated
under reduced pressure. The residue was purified by flash
chromatography on silica gel (n-hexane/CH2Cl2 from 100/0
to 85/15) to give pure 19 (493 mg, 68%) as a white solid.
Rf = 0.5 (Hexane/DCM 9/1). 1H-NMR (400 MHz, CDCl3):
ꢂ0.09 + ꢂ0.01 + ꢂ0.01 + 0.05 + 0.08 (5 s, 6 ꢁ 3 H, 6 ꢁ 6-
H + 6 ꢁ 6’-H + 6 ꢁ 6’’-H); 0.85 + 0.86 + 0.93 (3 s, 3 ꢁ 9 H,
9 ꢁ 8-H + 9 ꢁ 8’-H + 9 ꢁ 8’’-H); 1.75 (dt, 1 H, 5a-H, Jgem
=
13.8 Hz, J = 4.4 Hz); 2.15 (ddd, 1 H, 5b-H, Jgem = 13.8 Hz,
J = 8.3 Hz, J = 5.3 Hz); 3.65 (dd, 1 H, 2-H, J = 7.2 Hz, J = 3.7 Hz);
3.84–3.95 (m, 2 H, 3-H + 4-H); 3.98 (dd, 1 H, 1-H, J = 9.0 Hz,
J = 4.1 Hz); 6.59 (ddd, 1 H, 13-H, J = 7.9 Hz, J = 7.4 Hz,
J = 1.5 Hz); 7.00 (dd, 1 H, 15-H, J = 8.3 Hz, J = 1.5 Hz); 7.05–
7.10 (m, 1 H, 14-H); 7.20 (dd, 1 H, 12-H, J = 7.9 Hz, J = 1.5 Hz).
13C-NMR (100.61 MHz, CDCl3): ꢂ4.7 + ꢂ4.5 + ꢂ4.2 + ꢂ4.1 +
ꢂ4.0 + ꢂ3.9 (2 ꢁ 6-C + 2 ꢁ 6’-C + 2 ꢁ 6’’-C); 18.2 + 18.47 +
18.52 (7-C + 7’-C + 7’’-C); 26.1 + 26.2 + 26.3 (8-C + 8’-C + 8’’-
C); 41.0 (5-C); 66.5 (3-C); 72.8 (1-C); 77.4 (4-C); 78.7 (2-C);
113.6 (11-C); 117.3 (13-C); 119.0 (15-C); 127.9 (12-C);
129.0 (14-C); 144.5 (10-C). MS (ESI+): 586 [M + H]+.
5.29. (ꢃ)-(Z and E)-3-(4-isopropylbenzylidene)-1-
((1R,2S,3R,5S)-2,3,5-trihydroxycyclopentyl)indolin-2-one 16
TBAF (0.127 mL, 0.127 mmol, 1 M solution in THF) was
added to a stirred solution of 15Z and 15E mixture (30 mg,
0.041 mmol). The solvent was evaporated under reduced
pressure and taken up with CH2Cl2. The organic layer was
washed four times with water, the combined organic