A. Fürstner and M. Wuchrer
26b as a brown, amorphous solid (150 mg, 75%). [a]2D0 =ꢀ445 (c = 0.2,
CHCl3); 1H NMR (400 MHz, CD2Cl2): d=8.78 (d, J=9.0 Hz, NH, 1H),
4.90 (app sept [dddd], J=5.6 Hz, 1H), 4.55 (dd, J=10.8, 5.4 Hz, 1H),
4.47 (app t [dd], J=8.0 Hz, 1H), 4.35 (dd, J=10.1, 0.9 Hz, 1H), 4.32 (dd,
J=5.3, 2.5 Hz, 1H), 4.14 (dd, J=5.0, 2.8 Hz 1H), 4.10 (dd, J=7.9, 5.4 Hz,
1H), 4.03 (dd, J=10.5, 4.6 Hz, 1H), 3.96 (t, J=7.9 Hz, 1H), 3.89 (dd, J=
11.2, 2.8 Hz, 1H), 3.72 (m, 3H), 3.15–3.05 (m, 4H), 2.96 (s, 3H), 2.88 (s,
3H), 2.80 (s, 3H), 2.74 (s, 3H), 1.43 (s, 3H), 1.37 (s, 3H), 1.35 (s, 6H),
1.32 (s, 3H), 1.20 (s, 3H), 0.88 (s, 9H), 0.87 (s, 9H), 0.07 (s, 3H), 0.06 (s,
3H), 0.05 (s, 3H), 0.01(s, 3H); 13C NMR (100 MHz, CD2Cl2): d=166.4,
109.8, 108.8, 108.2, 93.4, 90.7, 82.8, 80.9, 79.5, 78.7, 75.2, 69.2, 65.2, 64.8,
64.6, 63.3, 57.5, 52.8, 52.6, 52.2, 51.9, 49.2, 28.3, 27.3, 26.9, 26.5, 26.3, 25.8,
25.8, 25.6, 18.4, ꢀ4.2, ꢀ4.5, ꢀ5.6, ꢀ5.7; IR (film): n˜ =2986, 2956, 2929,
2896, 2856, 1702, 1522, 1461, 1463, 1379, 1369, 1252, 1218, 1146, 1055,
1038, 1014, 960, 938, 831, 753 cmꢀ1; MS (EI): m/z (%): 1146 (3) [M +
ꢀCH3], 743 (10), 341 (16), 340 (100), 339 (13), 338 (72), 337 (45), 336
(34), 259 (9), 217 (12), 201 (20), 187 (21), 171 (23), 159 (9), 149 (11), 143
(14), 131 (15), 129 (39), 117 (75), 116 (12), 115 (82), 103 (21), 101 (57), 95
(12), 89 (21), 75 (65), 73 (71), 72 (25), 71 (12), 59 (10), 58 (69), 57 (14),
55 (10), 44 (16), 43 (42), 41 (9), 40 (38), 36 (14); HR-MS (ESI-pos): m/z:
calcd 1184.3632, found 1184.3614 [M ++Na]; elemental analysis calcd
(%) for: C 41.84, H 6.94, N 3.57; found: C 41.76, H 7.06, N 3.51.
(s, 6H), 1.43 (s, 3H), 1.39 (s, 3H), 1.31 (s, 3H), 1.29 (s, 3H), 0.87 (s, 9H),
0.87 (s, 9H), 0.08 (s, 6H), 0.07 (s, 3H), 0.06 (s, 3H); 13C NMR (100 MHz,
CD2Cl2): d=168.9, 130.2, 127.2, 127.1, 109.5, 108.2, 108.1, 79.7, 79.5, 78.7,
76.7, 76.3, 69.4, 68.1, 64.4, 62.8, 49.1, 27.6, 27.2, 27.2, 26.4, 25.8, 25.9, 25.3,
25.3, 18.5, 18.4, ꢀ4.1, ꢀ4.1, ꢀ5.4, ꢀ5.4; IR (film): n˜ =3435, 2986, 2954,
2930, 2886, 2857, 2854, 1773, 1714, 1613, 1472, 1463, 1382, 1372, 1251,
1220, 1148, 1055, 837, 779 cmꢀ1; MS (EI): m/z (%): 794 (6) [M ++H], 752
(13), 695 (19), 694 (35), 637 (22), 636 (48), 618 (10), 578 (21), 560 (13),
518 (11), 486 (16), 448 (14), 435 (15), 428 (20), 410 (11), 406 (13), 376
(13), 358 (14), 330 (12), 290 (12), 287 (16), 282 (11), 281 (14), 259 (17),
256 (12), 245 (17), 240 (23), 229 (21), 227 (10), 226 (26), 204 (12), 202
(27), 189 (14), 188 (30), 187 (40), 186 (10), 173 (13), 172 (11), 171 (17),
160 (16), 159 (15), 155 (12), 148 (14), 145 (12), 143 (13), 131 (25), 130
(16), 129 (39), 117 (36), 115 (21), 101 (41), 89 (35), 81 (11), 75 (51), 73
(100), 71 (11), 59 (10), 43 (22); HR-MS (ESI-pos): m/z: calcd 832.4100,
found 832.4106 [M ++Na].
Compound 29: HF·pyridine (70%, 400 mL) was added at 08C to a solu-
tion of compound 22 (419 mg, 0.540 mmol) in THF (2 mL) and pyridine
(400 mL) and the resulting mixture was stirred for 5 h. The reaction was
carefully quenched at 08C with aq. sat. NaHCO3 (4 mL). A standard ex-
tractive work up followed by flash chromatography of the crude product
(hexanes/EtOAc 2:1) furnished alcohol 29 as a colorless syrup (350 mg,
1
Osmate ester 26b: Prepared analogously from alkene 22. Brown amor-
phous solid (150 mg, 66%). 1H NMR (400 MHz, CD2Cl2): d=7.71(m,
2H), 7.56 (m, 2H), 5.12 (app t [dd], J=5.9 Hz, 1H), 4.95 (app t [dd], J=
5.1Hz, 1H), 4.71 (dd, J=10.1, 4.7 Hz, 1H), 4.66 (dd, J=10.4, 4.6 Hz,
1H), 4.62 (m, 1H), 4.53 (ddd, J=8.4, 6.8, 1.6 Hz, 1H), 4.38 (dd, J=9.3,
1.6 Hz, 1H), 4.06 (app t [dd], J=7.7 Hz, 1H), 3.95 (m, 2H), 3.87 (dd, J=
10.8, 4.0 Hz, 1H), 3.82 (dd, J=7.2, 4.8 Hz, 1H), 3.80 (m, 1H), 2.90–2.81
(m, 7H), 2.66 (s, 3H), 2.57 (s, 3H), 2.28 (s, 3H), 1.49 (s, 3H), 1.37 (s,
3H), 1.36 (s, 3H), 1.33 (s, 3H), 1.27 (s, 6H), 0.93 (s, 9H), 0.89 (s, 9H),
0.12 (s, 3H), 0.11 (s, 3H), 0.08 (s, 3H), 0.02 (s, 3H); 13C NMR (100 MHz,
CD2Cl2): d=169.6, 133.7, 132.9, 132.4, 132.2, 122.3, 122.2, 108.8, 107.8,
107.3, 90.3, 82.2, 79.5, 79.4, 76.8, 76.3, 75.1, 69.3, 64.4, 64.3, 63.8, 63.6,
53.1, 51.7, 51.4, 51.4, 28.3, 27.6, 27.3, 26.5, 26.2, 26.0, 25.5, 18.6, 18.4, ꢀ4.1,
ꢀ4.1, ꢀ5.3, ꢀ5.4; IR (film): n˜ =2979, 2955, 2929, 2856, 1711, 1463, 1461,
1379, 1252, 1218, 1149, 1117, 1056, 959, 837, 775 cmꢀ1; MS (ESI-pos):
m/z: 1148 [M ++H], 1170 [M ++Na]; HR-MS (ESI-pos): m/z: calcd
1148.4949, found 1148.4944 [M ++H].
98%). [a]2D0 =+53.0 (c = 0.45, CHCl3); H NMR (400 MHz, CDCl3): d=
7.81(dd, J=5.5, 3.1Hz, 2H), 7.70 (dd, J=5.5, 3.1Hz, 2H), 6.05 (app t
[dd], J=10.9 Hz, 1H), 5.81 (app t [dd], J=10.5 Hz, 1H), 5.25 (app t
[dd], J=10.2 Hz, 1H), 4.95 (dd, J=10.0, 4.8 Hz, 1H), 4.70 (dd, J=9.7,
7.2 Hz, 1H), 4.12 (m, 1H), 3.95–3.83 (m, 4H), 3.80 (dd, J=12.1, 2.9 Hz,
1H), 3.68 (app dt [ddd], J=7.5, 3.7 Hz, 1H), 3.62 (dd, J=12.1, 4.8 Hz,
1H), 1.75 (brs, 1H), 1.42 (s, 3H), 1.40 (s, 3H), 1.36 (s, 3H), 1.36 (s, 3H),
1.14 (s, 6H), 0.87 (s, 9H), 0.09 (s, 3H), 0.06 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=167.7, 134.0, 131.8, 131.5, 126.4, 123.4, 109.8, 108.6, 108.5,
80.8, 79.8, 75.8, 74.4, 71.4, 70.4, 64.7, 62.8, 52.0, 28.5, 27.2, 27.0, 25.9, 25.9,
25.7, 24.7, 18.4, 0.9, ꢀ4.2, ꢀ4.4; IR: n˜ =3476, 3060, 2986, 2954, 2934,
2886, 2857, 1773, 1714, 1613, 1470, 1383, 1372, 1255, 1220, 1152, 1087,
1053, 1036, 838, 780, 721 cmꢀ1; MS (EI): m/z (%): 646 (17) [M +ꢀCH3],
488 (24), 430 (12), 416 (12), 359 (10), 358 (41), 342 (13), 340 (18), 328
(12), 266 (21), 245 (12), 228 (27), 215 (20), 212 (14), 211 (15), 204 (18),
187 (44), 186 (10), 160 (12), 148 (13), 131 (100), 130 (17), 129 (23), 117
(20), 115 (10), 101 (57), 81 (10), 75 (23), 73 (45), 59 (71), 43 (27); HR-MS
(EI): calcd 684.3179, found 684.3178 [M ++Na]; elemental analysis calcd
(%) for: C 61.70, H 7.77, N 2.12; found: C 61.57, H 7.64, N 2.04.
Compound 27b: H2O (0.2 mL) and ethylenediamine (0.2 mL) were care-
fully added to a solution of the osmate ester 26b (321mg, 0.273 mmol) in
CH2Cl2 (4 mL) at 08C (exothermic!). The mixture was stirred for 36 h at
ambient temperature before it was diluted with chilled HCl (1m, 1mL).
A standard extractive work up followed by flash chromatography (hex-
anes/EtOAc 2:1) afforded diol 27b as a pale yellow syrup (110 mg,
71%). [a]2D0 =+14.0 (c = 0.25, CHCl3); 1H NMR (400 MHz, CD2Cl2):
d=7.50 (d, J=8.2 Hz, NH, 1H), 4.34 (d, J=9.2 Hz, 1H), 4.22 (m, 3H),
4.11 (dd, J=9.5, 5.1Hz, 1H), 3.86–3.76 (m, 7H), 3.62 (m, J=3.9 Hz,
1H), 1.44 (s, 3H), 1.39 (s, 6H), 1.37 (s, 3H), 1.35 (s, 3H), 1.26 (s, 3H),
0.90 (s, 9H), 0.87 (s, 9H), 0.08 (s, 6H), 0.07 (s, 6H); 13C NMR (100 MHz,
CD2Cl2): d=166.4, 109.8, 108.8, 108.2, 80.2, 79.6, 79.3, 78.6, 77.1, 76.1,
70.3, 67.9, 66.1, 63.0, 51.0 27.5, 27.1, 27.0, 26.2, 25.9, 25.2, 25.1, 18.4, ꢀ4.2,
ꢀ4.5, ꢀ5.6, ꢀ5.7; IR: n˜ =3428, 2986, 2955, 2930, 2896, 2857, 1718, 1512,
1472, 1463, 1381, 1371, 1256, 1221, 1149, 1092, 1055, 837, 780 cmꢀ1; MS
(EI): m/z (%): 808 (6) [M +ꢀCH3], 770 (10), 768 (23), 766 (20), 752 (13),
750 (11), 712 (22), 711 (19), 710 (52), 709 (18), 708 (46), 674 (10), 654
(19), 653 (16), 652 (45), 651 (15), 650 (39), 616 (10), 594 (11), 592 (12),
534 (10), 347 (10), 317 (13), 289 (15), 287 (14), 271 (11), 259 (45), 245
(16), 231 (11), 229 (17), 188 (10), 187 (52), 185 (11), 173 (18), 171 (21),
159 (17), 155 (13), 145 (14), 143 (13), 131 (28), 130 (10), 129 (37), 117
(42), 115 (20), 101 (53), 95 (9), 89 (33), 81 (14), 75 (52), 73 (100), 71 (11),
59 (13), 43 (26), 40 (27); HR-MS (ESI-pos): m/z: calcd 846.2981, found
846.2994 [M ++Na].
Compound 30: DMSO (39 mL, 0.549 mmol) was added to a solution of
oxalyl chloride (14 mL, 0.165 mmol) in CH2Cl2 (3 mL) at ꢀ788C and the
resulting mixture was stirred for 30 min before a solution of alcohol 29
(74 mg, 0.112 mmol) in CH2Cl2 (1mL) was introduced. Stirring was con-
tinued for 30 min before Et3N (150 mL, 1.1 mmol) was added at ꢀ788C
and the resulting mixture was allowed to warm to 08C over the course of
20 h. The reaction was quenched with aq. HCl (2m) at ꢀ108C and diluted
with Et2O (10 mL). The organic layer was successively washed with aq.
sat. NaHCO3, water and brine (5 mL each) before it was dried (Na2SO4)
and evaporated to give aldehyde 30 as a yellow syrup which was used in
the next step without further purification (55 mg, 75%). [a]2D0 =+14.0 (c
=
0.25, CHCl3); 1H NMR (400 MHz, CDCl3): d=9.76 (d, J=0.7 Hz,
1Hz), 7.82 (dd, J=5.6, 3.1Hz, 2H), 7.70 (dd, J=5.5, 3.1Hz, 2H), 6.07
(app t [dd], J=11.2 Hz, 1H), 5.92 (app t [dd], J=10.3 Hz, 1H), 5.29 (app
t [dd], J=10.2 Hz, 1H), 5.06 (dd, J=9.8, 4.8 Hz, 1H), 4.95 (dd, J=10.1,
4.7 Hz, 1H), 5.53 (dd, J=4.9, 0.6 Hz, 1H), 3.93–3.83 (m, 4H), 3.66 (ddd,
J=6.7, 4.8, 3.7 Hz, 1H), 1.47 (s, 6H), 1.39 (s, 3H), 1.34 (s, 3H), 1.32 (s,
3H), 1.11 (s, 3H), 0.86 (s, 9H), 0.09 (s, 3H), 0.06 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=200.2, 167.6, 134.1, 132.5, 131.7, 126.0, 123.0,
112.3, 108.7, 108.1, 83.3, 79.9, 75.9, 75.2, 71.3, 70.5, 64.9, 51.8, 28.5, 27.2,
26.6, 29.9, 25.9, 25.7, 24.7, 18.4, ꢀ4.2, ꢀ4.4; IR: n˜ =3058, 2987, 2935,
2899, 2857, 1773, 1715, 1613, 1469, 1382, 1254, 1219, 1153, 1071, 1036,
840, 780, 721cm ꢀ1; MS (ESI-pos): 682 [M ++Na]; HR-MS (EI): m/z:
calcd 682.3023, found 682.3028 [M ++Na]; elemental analysis calcd (%)
for: C 61.89, H 7.49, N 2.12; found: C 61.78, H 7.41, N 2.08.
Compound 27a: Prepared analogously from osmate ester 26a as a color-
less foam (51mg, 66%). 1H NMR (400 MHz, CD2Cl2): d=7.48 (m, 2H),
7.42 (m, 2H), 4.63 (m, 1H), 4.47–4.43 (m, 2H), 4.27 (dd, J=10.7, 2.7 Hz,
1H), 4.10 (dd, J=9.4, 5.3 Hz, 1H), 3.99–3.95 (m, 4H), 3.90–3.87 (m, 2H),
3.83–3.82 (m, 2H), 3.75 (dd, J=9.4, 7.4 Hz, 1H), 3.66–3.58 (m, 1H), 1.45
Compound 32: An aq. solution of RuCl3 (0.1m, 1 5mL, 0.0015 mmol) was
added to a clear solution of NaIO4 (13 mg, 0.061 mmol) and FeCl2·4H2O
86
ꢁ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2006, 12, 76 – 89