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Can. J. Chem. Vol. 79, 2001
(7Cp-CH), 74.0, 70.5, 43.0, 33.0–25.8 (PCy2, CHMeP),
24.2, 17.6, 14.2, –2.4, –2.5. 31P NMR (101.3 MHz, CDCl3)
d: 16.0 (d, J = 33.5, PCy2), –26.4 (d, J = 33.5, PPh2). Anal.
calcd. for C90H117N3O2P4Si2Fe2: C 69.09, H 7.54, N 2.69;
found: C 68.83, H 7.72, N 2.89.
DMSO-d6, 100°C) d: 18.2 (d, J = 35.4, PCy2), –23.3 (d, J =
35.4, PPh2). Anal. calcd. for C374H476N12O12P16Si8Fe8:
C 69.12, H 7.38, N 2.59; found: C 69.19, H 7.46, N 2.39.
1-(tert-Butyldimethylsilyloxy)-3,5-bis{1-oxo-2-aza-2-[3,5-
bis{6-[(SP)-1-diphenylphosphino-2-[1R-(dicyclohexyl-
phosphino)ethyl]-1>-ferrocenyl]-6-dimethyl-1-oxo-2-aza-6-
silahexyl}phenyl]}benzene ((R)-(S)-22a)
6-Cascade:benzene[3-1,3,5]:(5-(1-oxo-2-aza)-1,3-
phenylene):1>-(1-dimethyl-6-oxo-5-aza-1-silahexyl)-(SP)-1-
diphenylphosphino-2-[1R-(dicyclohexylphosphino)-
ethyl]ferrocene ((R)-(S)-18)
(R)-(S)-22a was prepared at rt from (R)-(S)-14 (856 mg,
547 mol), NEt3 (280 L, 2.00 mmol), 4-(pyrrolidino)-
pyridine (5 mg, 33.7 mol) in 20 mL of toluene, and 15
(82.9 mg, 249 mol) in 5 mL of toluene according to the
general procedure described above (5.5 h stirring) to afford,
after silica gel flash chromatography (hexane – ethyl acetate
(1:1) + 1% NEt3), (R)-(S)-22a (746 mg, 220 mol, 88%) as
an orange powder; mp 128–133°C. [a]D = –255 (c = 0.84,
CHCl3). MALDI-LRMS m/z: 3391 ([M]+), 3194 ([M –
HPCy2]+), 2918 ([M – C5H3(PPh2)(CH(Me)PCy2)]+). IR
(KBr) (cm–1): 2925, 2849, 1652 (C=O). 1H NMR (300 MHz,
DMSO-d6, 80°C,) d: 10.35 (s, 2H), 8.33 (d, J = 1.3, 4H),
8.29 (m, 1H), 8.15 (t, J = 5.5, 4H), 7.91 (m, 2H), 7.64 (m,
10H), 7.40 (m, 12H), 7.17 (m, 20H), 4.37 (m, 4H), 4.34 (m,
4H), 4.30 (m, 4H), 4.09 (m, 4H), 4.07 (m, 4H), 3.74 (m,
4H), 3.31 (m, 4H), 3.23 (m, 12H), 1.9–0.9 (m, 108H), 1.05
(s, 9H), 0.58 (m, 8H), 0.31 (s, 6H), 0.15 (s, 12H), 0.08 (s,
12H). 13C NMR (75.5 MHz, DMSO-d6, 80°C) d: 166.0,
165.3, 157.8, 141.5–127.1 (PPh2), 136.5, 122.2, 121.0,
118.0, 117.8, 101.5, 74.2–69.1 (7Cp-CH), 73.8, 70.4,
42.7, 32.8–25.7 (PCy2, CHMeP), 26.2, 24.0, 17.8, 16.9,
14.0, –2.1, –3.1. 31P NMR (101.3 MHz, CDCl3) d: 15.9 (d,
J = 34.4, PCy2), –26.4 (d, J = 34.4, PPh2). Anal. calcd. for
C194H250N6O7P8Si5Fe4: C 68.74, H 7.43, N 2.48; found:
C 68.46, H 7.56, N 2.46.
(R)-(S)-18 was prepared at 0°C from (R)-(S)-14 (751 mg,
480 mol), NEt3 (180 L, 1.30 mmol), 4-(pyrrolidino)-
pyridine (5 mg, 33.7 mol) in 10 mL of toluene, and 6
(35.4 mg, 133 mol) in 5 mL of toluene according to the
general procedure described above (warmed to rt and stirred
overnight) to afford, after silica gel flash chromatography
(hexane – ethyl acetate (1:1) + 5% NEt3), (R)-(S)-18
(496 mg, 102 mol, 77%) as an orange powder; mp 125–
130°C. [a]D = –255 (c = 0.94, CHCl3). MALDI-LRMS m/z
(%): 4850 ([M]+), 4653 ([M – HPCy2]+), 4377 ([M –
C5H3(PPh2)(CH(Me)PCy2)]+). IR (KBr) (cm–1): 2923, 2849,
1
1654 (C=O). H NMR (300 MHz, DMSO-d6, 100°C) d:
10.50 (s, 3H), 8.79 (s, 3H), 8.36 (d, J = 1.4, 6H), 8.01 (t, J =
5.5, 6H), 7.97 (t, J = 1.4, 3H), 7.63 (m, 12H), 7.38 (m,
18H), 7.18 (m, 30H), 4.37 (m, 6H), 4.33 (m, 6H), 4.30 (m,
6H), 4.08 (m, 12H), 3.77 (m, 6H), 3.34 (m, 6H), 3.24 (m,
18H), 1.9–0.9 (m, 162H), 0.60 (m, 12H), 0.15 (s, 18H), 0.09
(s, 18H). 13C NMR (75.5 MHz, DMSO-d6, 100°C) d: 166.0,
164.8, 141.4–127.1 (PPh2), 139.1, 136.2, 131.4, 129.9,
122.3, 121.2, 101.6, 74.1–69.1 (7Cp-CH), 74.1, 71.2, 42.8,
33.0–26.2 (PCy2, CHMeP), 24.1, 17.1, 14.1, –2.0, –2.1. 31P
NMR (121.5 MHz, DMSO-d6, 100°C) d: 18.2 (d, J = 35.5,
PCy2), –23.4 (d, J = 35.5, PPh2). Anal. calcd. for
C279H351N9O9P12Si6Fe6: C 69.09, H 7.29, N 2.60; found:
C 69.17, H 7.50, N 2.56.
1-Hydroxy-3,5-bis{1-oxo-2-aza-2-[3,5-bis{6-[(SP)-1-
diphenylphosphino-2-[1R-(dicyclohexylphosphino)ethyl]-
1>-ferrocenyl]-6-dimethyl-1-oxo-2-aza-6-silahexyl}-
8-Cascade:tricyclo[3.3.1.13,7]decane[4-1,3,5,7]:(5-(1-oxo-
2-aza)-1,3-phenylene):1>-(1-dimethyl-6-oxo-5-aza-1-
silahexyl)-(SP)-1-diphenylphosphino-2-[1R-(dicyclohexyl-
phosphino)ethyl]ferrocene ((R)-(S)-20)
phenyl]}benzene ((R)-(S)-22)
To a solution of the silylether (R)-(S)-22a (1.05 g,
310 mol) in 20 mL of THF was added a 1 M solution of
tetrabutylammonium fluoride in THF (0.46 mL, 0.46 mmol).
After stirring at rt for 20 min the solution was treated with
sat. NH4Cl solution. The aqueous phase was extracted with
Et2O, the organic extracts were washed water (3 times),
dried over anhydrous magnesium sulfate, and the solvent
was removed in vacuo. The product was purified by silica
gel flash chromatography (first hexane – ethyl acetate
(3:1) + 5% NEt3, to elute impurities, then ethyl acetate to
elute the product) to yield (R)-(S)-22 as an orange powder
(890 mg). This product contains 2.5 equivalents of H2O per
molecule of product, which means a yield of 878 mg
(268 mol, 86%); mp 148–154°C. [a]D = –257 (c = 0.745,
CHCl3). MALDI-LRMS m/z: 3276 ([M]+), 3078 ([M –
HPCy2]+), 2803 ([M – C5H3(PPh2)(CH(Me)PCy2)]+). IR
(KBr) (cm–1): 2924, 2848, 1653 (C=O). 1H NMR (300 MHz,
DMSO-d6, 100°C) d: 10.17 (s, 2H), 9.70 (s, 1H), 8.31 (d,
J = 1.4, 4H), 8.06 (m, 1H), 7.98 (t, J = 5.5, 4H), 7.93 (m,
2H), 7.64 (m, 8H), 7.58 (m, 2H), 7.38 (m, 12H), 7.16 (m,
20H), 4.37 (m, 4H), 4.34 (m, 4H), 4.30 (m, 4H), 4.09 (m,
8H), 3.77 (m, 4H), 3.34 (m, 4H), 3.23 (m, 12H), 1.9–0.9 (m,
108H), 0.58 (m, 8H), 0.15 (s, 12H), 0.09 (s, 12H). 13C NMR
(R)-(S)-20 was prepared at rt from (R)-(S)-14 (700 mg,
477 mol), NEt3 (0.84 mL, 6.0 mmol), 4-(pyrrolidino)-
pyridine (5 mg, 33.7 mol) in 10 mL of toluene, and 7
(93.2 mol, in situ from 1,3,5,7-adamantanetetracarboxylic
acid (29.1 mg)) in 4 mL of toluene according to the general
procedure described above (stirred overnight) to afford, after
silica gel flash chromatography (hexane – ethyl acetate
(1:1) + 1% NEt3), (R)-(S)-20 (348 mg, 53.5 mol, 57%) as
an orange powder; mp 112–117°C. [a]D = –264 (c = 1.21,
CHCl3). MALDI-LRMS m/z: 6494 ([M]+), 6297 ([M –
1
HPCy2]+). IR (KBr) (cm–1): 2924, 2849, 1655 (C=O). H
NMR (300 MHz, DMSO-d6, 100°C) d: 9.28 (s, 4H), 8.20 (d,
J = 1.4, 8H), 7.95 (t, J = 5.6, 8H), 7.90 (t, J = 1.4, 4H), 7.62
(m, 16H), 7.37 (m, 24H), 7.15 (m, 40H), 4.36 (m, 8H), 4.31
(m, 8H), 4.29 (m, 8H), 4.06 (m, 16H), 3.76 (m, 8H), 3.29
(m, 8H), 3.21 (m, 24H), 2.24 (s, 12H), 1.9–0.9 (m, 216H),
0.58 (m, 16H), 0.14 (s, 24H), 0.07 (s, 24H). 13C NMR
(75.5 MHz, DMSO-d6, 100°C) d: 174.6, 166.1, 141.4–127.1
(PPh2), 139.2, 135.9, 122.3, 120.9, 101.6, 74.1–69.1 (7Cp-
CH), 74.0, 71.2, 43.6, 42.8, 38.6, 33.0–26.2 (PCy2, CHMeP),
24.0, 17.1, 14.1, –2.0, –2.1. 31P NMR (121.5 MHz,
© 2001 NRC Canada