206
P.D. Woodgate et al. / Journal of Organometallic Chemistry 560 (1998) 197–209
9
3.94, 94.54, 98.58, 101.46 (C-2%), 119.28 (C-1%), 233.48
100% yield. Recrystallization from hexanes/diethyl
+
(
(
Cr(CO) ). m/z 467 (M , 51%), 452 (M-Me, 2), 411
M-2CO, 2), 383 (M-3CO, 62), 367 (C H CrNOSi,
ether afforded yellow crystals, m.p. 231°C (Found:
3
+
M , 579.1615. C H CrNO P. Calc.: M, 579.1630).
19
29
32 34
4
M-3COꢁMeꢁH, 72), 351 (C H CrNOSi, M-3COꢁ2-
wmax (CDCl ) 2966, 2943, 2872, 1967, 1879, 1475, 1434,
1
8
25
3
Meꢁ2H, 44), 326 (M-3COꢁC H , 72), 311 (C H
1411, 1399, 1358, 1318, 1224, 1213, 1172, 1114,
4
9
15 21
−
1
CrNOSi, M-3COꢁC H ꢁMe, 100), 286 (Me SiC H
1061, 1038, 1009, 986, 699 cm . lH 0.58–0.63 (m,
1H), 0.86–1.06 (m, 2H), 1.09–1.24 (m, 11H), 1.49–
1.60 (m, 2H), 2.00–2.03 (m, 1H), 2.36 (ddd, J 2.7, 10,
10 Hz, 1H, H-3a), 2.64 (ddd, J 3.5, 10, 10 Hz, 1H,
H-7a), 4.72 (ddd, J 1, 1, 6 Hz, 1H, H-3%), 5.20 (ddd, J
1, 6, 6 Hz, 1H, H-5%), 5.49 (dddd, J 1, 1, 6, 6 Hz, 1H,
H-4%), 5.94 (d, J 2 Hz, 1H, H-2), 6.20 (ddd, J 1, 2.7, 6
Hz, 1H, H-6%), 7.29–7.35 (m, 10H). lC 23.89 (C-5),
4
9
3
6
4
Cr(CO) , 29), 252 (M-3COꢁC H ꢁMe SiꢁH, 48), 244
3
4
9
3
(
7
M-3COꢁC H ꢁC H , 15), 229 (Me SiC H COCr, 20),
4
9
6
10
3
6
4
3 (SiMe , 15), 57 (C H , 18), 52 (Cr, 77).
3 4 9
3
.6. Tricarbonyl[(3a,7a-trans)-octahydro-3-(t-butyl)-2-
6
(p -2%-methylthiophenyl)benzoxazole]chromium(0) (5)
The general procedure was the same as described
24.81 (C-6), 28.05 (ꢂNCMe ), 28.85 (C-4), 33.71 (C-7),
3
for the preparation of 6. Complex 1 (215 mg, 0.54
54.66 (ꢂNCMe ), 64.73 (C-3a), 79.92 (C-7a), 89.43 (d,
3
−
1
mmol) was treated with butyllithium (2.47 mol l
hexanes, 0.28 ml, 0.69 mmol) and dimethyl disulfide
0.3 ml, 3.3 mmol) to give the title complex in 100%
in
J 7 Hz), 92.18 (C-2), 92.48, 94.34 (d, J 5 Hz), 97.97
(d, J 3 Hz), 104.06 (d, J 30 Hz, C-2%), 119.22 (d, J 20
Hz, C-1%), 128.15 (d, J 7 Hz, 2×ArH m), 128.38 (d, J
5 Hz, 2×ArH m), 129.23 (2×ArH p), 132.68 (d, J
19 Hz, 2×ArH o), 134.80 (d, J 20 Hz, 2×ArH o),
(
yield. Recrystallization from hexanes/diethyl ether af-
forded yellow needles, m.p. 178.4–179.5°C. (Found:
C, 57.1; H, 6.1; N, 3.2: C H CrNO S. Calc.: C, 57.1;
2
1
27
4
136.00 (d, J 14 Hz, 2×ArH ipso), 232.60 (Cr(CO) ).
3
+
+
H, 6.2; N, 3.2%). (Found: M , 441.1068;
C H CrNO S. Calc.: M, 441.1066). w (CDCl3)
m/z 579 (M , 5%), 495 (M-3CO, 85), 438 (M-
2
1
27
4
max
3COꢁC H , 100), 397 (Ph PC H Cr(CO) , 5), 386 (M-
4
9
2
6
4
3
2
1
1
972, 2943, 2875, 1968, 1890, 1479, 1459, 1445, 1411,
392, 1362, 1319, 1227, 1212, 1169, 1115, 1062, 1038,
3COꢁC H ꢁCr, 11), 313 (Ph PC H Cr, 6), 261
4
9
2
6
4
(Ph PC H , 4), 252 (M-3COꢁPPh ꢁC H ꢁH, 5), 212
2
6
4
2
4
9
−
1
009, 970 cm . lH 1.11–1.17 (m, 1H), 1.18 (s, 9H,
(C H Cr(CO) , 9), 52 (Cr, 72).
6 4 3
NC(CH ) ), 1.26–1.41 (m, 2H), 1.54 (dddd, J 3.8, 11.7,
3
3
11.7, 11.7 Hz, 1H), 1.70–1.81 (m, 2H), 2.00–
2.04 (m, 1H), 2.10–2.14 (m, 1H), 2.41 (s, 3H, SCH3),
2.51 (ddd, J 2.9, 10, 10 Hz, 1H, H-3a), 3.07 (ddd, J
3.5, 10, 11.3 Hz, 1H, H-7a), 5.09 (dd, J 1, 6 Hz, 1H,
3
.8. Tricarbonyl[(3a,7a-trans)-octahydro-3-(t-butyl)-2-
6
(p -2%-trimethylstannylphenyl)benzoxazole]chromium(0)
8)
(
H-3%), 5.13 (ddd, J 1, 6, 6 Hz, 1H), 5.49 (ddd, J 1, 6,
Hz, 1H), 5.69 (s, 1H, H-2), 6.31 (dd, J 1, 6 Hz, 1H,
The general procedure was the same as described
6
for the preparation of 6. Complex 1 (200 mg, 0.51
H-6%). l 16.38 (ꢁSMe), 24.00 (C-5), 24.83 (C-6), 27.86
C
−
1
mmol) was treated with butyllithium (2.47 mol l
in
(
6
9
ꢂNCMe ), 29.91 (C-4), 33.63 (C-7), 54.95 (ꢂNCMe ),
3
3
hexanes, 0.27 ml, 0.67 mmol) and chlorotrimethylstan-
nane (200 mg, 1.0 mmol, dissolved in THF (2 ml).
Column chromatography of the crude product on sil-
ica gel with hexanes containing increasing quantities
of diethyl ether gave the title complex (265 mg, 0.48
mmol, 94%). Recrystallization from hexanes afforded
4.89 (C-3a), 79.66 (C-7a), 86.21, 86.42, 88.94 (C-2),
4.72, 95.05, 112.49 (C-1%), 116.53 (C-2%), 232.88
+
(
Cr(CO) ). m/z 441 (M , 11%), 385 (M-2CO, 23), 357
3
(
3
M-3CO, 60), 300 (M-3COꢁC H , 100), 285 (M-
4
9
COꢁC H ꢁMe, 39), 275 (M-3COꢁC H , 6), 259
4
9
6
10
(
2
MeSC H Cr(CO) , 10), 253 (M-3COꢁC H ꢁSMe, 24),
6
4
3
4
9
+
yellow needles, m.p. 138–139 °C (Found: M ,
13 (C H Cr(CO) , 14), 201 (MeSC H CrCN, 8), 58
6 5 3 6 4
5
5
1
1
57.0849/559.0854;
C H CrNO Sn.
Calc.:
M,
(
C H N, 17), 57 (C H , 19), 52 (Cr, 63), 41 (C H ,
23 33
4
3
8
4
9
3
5
57.0831/559.0837). wmax (CDCl ) 2972, 2946, 2872,
25).
3
961, 1878, 1475, 1458, 1448, 1397, 1381, 1361, 1320,
256, 1213, 1177, 1115, 1060, 1038, 1009, 978, 942,
3
.7. Tricarbonyl[(3a,7a-trans)-octahydro-3-(t-but-
−
1
6
864, 830, 772 cm . lH 0.34 (s, 9H, Sn(CH ) ), 1.13
yl)-2-(p -2%-diphenylphosphinophenyl)benzoxazole]-
chromium(0) (7)
3 3
(
s, 9H, NC(CH ) ), 1.13–1.33 (m, 3H), 1.52 (dddd, J
3 3
3
1
2
.8, 11.6, 11.6, 11.6 Hz, 1H), 1.65–1.69 (m, 1H),
.74–1.78 (m, 1H), 1.97–2.07 (m, 2H), 2.46 (ddd, J
.8, 10, 10 Hz, 1H, H-3a), 2.96 (ddd, J 3.5, 10, 11.4
Hz, 1H, H-7a), 5.24 (dd, J 1.2, 6 Hz, 1H, H-3%), 5.31
s, 1H, H-2), 5.33 (ddd, J 1.2, 6, 6 Hz, 1H), 5.42 (ddd,
J 1.2, 6, 6 Hz, 1H), 6.14 (dd, J 1.2, 6 Hz, 1H,
The general procedure was the same as described
for the preparation of 6. Complex 1 (260 mg, 0.66
−
1
mmol) was treated with butyllithium (2.47 mol l
in
(
hexanes, 0.34 ml, 0.84 mmol) and chlorodiphenylphos-
phine (0.48 ml, 2.67 mmol) to give the title complex in