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S. Malfait et al. / Tetrahedron: Asymmetry 9 (1998) 2595–2610
4.6. General procedure for the condensation of the 2-picolyllithium
To a solution of α-picoline (45 µl, 0.45 mmol) in dry THF (5 ml) was added phenyllithium (240 µl,
.8 M in cyclohexane, 0.43 mmol) at room temperature. After 1.5 h, the red solution of 2-picolyllithium
1
was introduced into a solution of ketone (0.37 mmol) in dry THF (10 ml) at −78°C. The reactive mixture
was stirred and allowed to reach room temperature. After the appropriate reaction time, the mixture was
quenched slowly by a saturated aqueous sodium hydrogenocarbonate solution (10 ml), diluted with water
(
10 ml) and extracted with Et O. The solvent was evaporated under vacuum and the crude product was
2
purified by silica gel column chromatography.
4.6.1. (+)-(S,1S)-Tricarbonyl[1-(2-picolyl)indanol]chromium 8
Following the general procedure, 2-picolyllithium was introduced to a solution of ketone (+)-(S)-2
(99 mg, 0.37 mmol) in THF (10 ml). The solution was stirred at room temperature for 15 h. Work-up
and column chromatography gave the complex (+)-(S,1S)-20 (35 mg, 26%) as a yellow oil; [α] =+177
D
1
(
c=2.05, Et O); H NMR (CDCl ) 8.52 (m, 1H), 7.60 (m, 1H), 7.26 (m, 1H), 7.00 (m, 1H), 5.35 (t, J 5.8
2
3
Hz, 1H), 5.21 (d, J 6.3 Hz, 1H), 5.14 (d, J 6.3 Hz, 1H), 5.00 (t, J 5.6 Hz, 1H), 3.12 (d, J 14 Hz, 1H), 2.91
+
(
d, J 14 Hz, 1H), 2.75 (m, 2H), 2.12 (m, 2H); MS (m/z) 361 (M , 31), 333 (17), 305 (17), 277 (75), 275
(
100); anal. calcd for C H CrNO : C, 59.84; H, 4.18; N, 3.88. Found C, 60.03; H, 4.22; N, 3.92.
18
15
4
4.6.2. (+)-(S,1S)-Tricarbonyl[1-(2-picolyl)-1-tetralol]chromium 12
Following the general procedure, 2-picolyllithium was introduced to a solution of ketone (+)-(S)-4
(104 mg, 0.37 mmol) in THF (10 ml). The solution was stirred at room temperature for 1.5 h. Work-up
and column chromatography gave the complex (+)-(S,1S)-12 (90 mg, 68%) as a yellow oil; [α] =+40
D
1
(
c=0.524, Et O); H NMR (CDCl ) 8.51 (d, J 4.0 Hz, 1H), 7.60 (t, J 4.0 Hz, 1H), 7.24 (t, J 4.0 Hz, 1H),
2
3
7
.00 (d, J 4.0 Hz, 1H), 5.87 (t, J 6.0 Hz, 1H), 5.46 (d, J 6.0 Hz, 1H), 5.10 (m, 2H), 3.12 (s, 2H), 2.71 (m,
+
2H), 1.80 (m, 4H); MS (m/z) 375 (M , 25), 319 (30), 291 (22), 271 (33); anal. calcd for C H CrNO:
19
17
C, 60.80; H, 4.57; N, 3.73. Found: C, 60.89; H, 4.32; N, 3.82.
4
.6.3. (+)-(S,1S)-1,2-[α-Hydroxy-α-(2-picolyl)tetramethylene]ferrocene 15
Following the general procedure, 2-picolyllithium was introduced to a solution of ketone (+)-(S)-6
99 mg, 0.39 mmol) in THF (10 ml). The solution was stirred at room temperature for 4 h. Work-up
(
and column chromatography gave the complex (+)-(S,1S)-15 (87 mg, 64%) as a yellow oil; [α] =+148
D
1
(
c=0.87, Et O); H NMR (CDCl ) 8.52 (dd, J 7.6 Hz and 1.8 Hz, 1H), 7.61 (t, J 7.6 Hz, 1H), 7.15 (m,
2
3
2
H), 4.20 (s, 5H), 4.11 (s, 1H), 4.00 (s, 1H), 3.91 (s, 1H), 3.10 (d, J 13.9 Hz, 1H), 3.02 (d, J 13.9 Hz,
+
1H), 2.65 (m, 1H), 2.21 (m, 1H), 1.89 (m, 2H), 1.57 (m, 2H); MS (m/z) 347 (M , 100), 282 (6), 262
(
100), 254 (80); anal. calcd for C H FeNO: C, 69.14; H, 6.10; N, 4.03. Found C, 69.41; H, 6.30; N,
20 21
4.02.
4.6.4. (+)-(S)-(E)-α-Pyridinyl-propylidene[3](1,2)-ferrocenophane 18
A solution of complex (+)-(S,1S)-15 (200 mg, 0.61 mmol) in Et O (50 ml) was added to a solution of
2
HCl (1 N, 10 ml). After stirring for 5 min, the solution was extracted with Et O. The red aqueous layer
2
was neutralized by an addition of potassium carbonate, extracted with Et O. The solvent was removed by
2
vacuum. The product was purified by column chromatography to yield complex (+)-(S,1S)-18 (161 mg,
1
8
(
0%) as red oil. [α] =+748 (c=1.87, CHCl ); H NMR (CDCl ) 8.58 (s, 1H), 7.61 (t, J 5 Hz, 1H), 7.20
D
3
3
s, 1H), 7.00 (m, 1H), 6.75 (s, 1H), 4.63 (s, 1H), 4.31 (s, 1H), 4.20 (s, 1H), 4.12 (s, 5H), 3.39 (m, 1H),